CN112551909A - Method for etching and manufacturing ultra-thin glass - Google Patents
Method for etching and manufacturing ultra-thin glass Download PDFInfo
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- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
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- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous glass
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- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
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- 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
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- C03C2217/70—Properties of coatings
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- 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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/732—Anti-reflective coatings with specific characteristics made of a single layer
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- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
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- 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
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/365—Coating different sides of a glass substrate
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
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Abstract
The invention discloses a method for etching and manufacturing ultrathin glass, which comprises the following steps: etching with etching solution A and etching solution B, respectively, using Ca2+、Mg2+After surface modification, performing surface treatment by using a hydrophobic repair liquid; the etching solution A takes water as a solvent and comprises the following components in molar concentration: 1.5-3 mol/L hydrofluoric acid, 0.5-1.5 mol/L hydrochloric acid, 1.0-1.5 mol/L sodium fluosilicate and 0.1-0.2 mol/L sodium dodecyl sulfate; the etching solution B takes water as a solvent and comprises the following components in molar concentration: 0.5-1.5 mol/L hydrofluoric acid, 0.3-0.8 mol/L hydrochloric acid, 0.5-0.8 mol/L sodium fluosilicate and 0.1-0.2 mol/L sodium dodecyl sulfate; the hydrophobic repairing liquid comprises the following components in parts by mass: 40-50 parts of aqueous fluorocarbon emulsion, 1-3 parts of hydrophobic agent, 5-7 parts of sodium silicate, 2-3 parts of sodium fluoride, 10-15 parts of nano titanium oxide sol and 15-long range silica sol20 parts of structure directing agent, 3-5 parts of amino silane coupling agent, 1-2 parts of emulsifying agent and 0.5-2 parts of emulsifying agent. The invention realizes the repair of the surface defect position of the etched glass substrate, and improves the structural stability and the mechanical strength; but also endows the glass with flexibility and prevents the ultrathin glass from cracking.
Description
Technical Field
The invention belongs to the technical field of glass etching, and particularly relates to a method for manufacturing ultrathin glass by etching.
Background
Ultra-thin glass is a reflection of global consumer electronics products tending to be light and thin, and is gradually developing towards more ultra-thin in the aspects of smart phones and notebook computers. With the matching maturity of related software and hardware industries and higher requirements on thinning application, the ultrathin glass is also widely applied to mobile phone cover plates.
Because ultra-thin glass mainly adopts hydrofluoric acid to carry out the chemical etching attenuate, but can make the original defect on glass surface further exposed and enlargeing, cause glass surface stress to distribute inhomogeneous, when being used for cell-phone touch-sensitive screen apron, weaken the compressive strength and the toughness of glass base plate, very easily appear the problem that the broken screen was broken, the broken screen also is the most common problem that appears in the smart mobile phone use.
Based on the above, the invention discloses a method for etching and manufacturing ultrathin glass, so as to produce ultrathin glass which simultaneously satisfies the requirements of lightness, thinness, high compressive strength and toughness and is not easy to break.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a method for etching ultra-thin glass.
The technical scheme of the invention is summarized as follows:
the method for etching and manufacturing the ultra-thin glass comprises the following steps: etching with etching solution A and etching solution B, respectively, using Ca2+、Mg2 +After surface modification, performing surface treatment by using a hydrophobic repair liquid;
the etching solution A takes water as a solvent and comprises the following components in molar concentration: 1.5-3 mol/L hydrofluoric acid, 0.5-1.5 mol/L hydrochloric acid, 1.0-1.5 mol/L sodium fluosilicate and 0.1-0.2 mol/L sodium dodecyl sulfate;
the etching solution B takes water as a solvent and comprises the following components in molar concentration: 0.5-1.5 mol/L hydrofluoric acid, 0.3-0.8 mol/L hydrochloric acid, 0.5-0.8 mol/L sodium fluosilicate and 0.1-0.2 mol/L sodium dodecyl sulfate;
the hydrophobic repairing liquid comprises the following components in parts by mass: 40-50 parts of water-based fluorocarbon emulsion, 1-3 parts of hydrophobic agent, 5-7 parts of sodium silicate, 2-3 parts of sodium fluoride, 10-15 parts of nano titanium oxide sol, 15-20 parts of nano silicon oxide sol, 3-5 parts of structure directing agent, 1-2 parts of aminosilane coupling agent and 0.5-2 parts of emulsifier;
the method specifically comprises the following steps:
s1: cleaning: wiping a glass substrate with the thickness of 200-400 mu m with absolute ethyl alcohol, removing surface grease, washing with clear water for 2-3 times, and naturally drying;
s2: first etching treatment: soaking the glass substrate cleaned in the S1 in the etching solution A, carrying out ultrasonic treatment at 25 ℃, carrying out etching thinning treatment until the thickness of the glass substrate is 100-150 mu m, and washing and drying;
s3: and (3) second etching treatment: placing the glass substrate etched in S2 in an etching tank, etching and thinning the glass substrate to 20-30 μm in thickness by using etching solution B, and washing and drying;
s4: surface modification: soaking the etched glass substrate of S3 in CaCl with the concentration of 0.05-0.2 mol/L2、0.05～0.2mol/L MgCl2Carrying out ultrasonic treatment for 0.5-1 h at 40-60 ℃, taking out, and drying at 80 ℃;
s5: surface treatment: and (3) uniformly coating the hydrophobic repairing liquid on the surface of the glass substrate modified by the S4 surface, controlling the thickness of the single-side coating to be 0.5-4 mu m, and curing and drying at 60-120 ℃ for 6-10 h to obtain the ultrathin glass.
Preferably, the solid content of the aqueous fluorocarbon emulsion is 30-40%.
Preferably, the hydrophobic agent is one or more of tridecafluorooctyl triethoxysilane, heptadecafluorodecyl triethoxysilane, octamethylcyclotetrasiloxane and trifluoropropylmethylsilicone oil.
Preferably, the solid content of the nano titanium oxide sol is 10-15%, and the particle size of the nano titanium oxide is 5-20 nm.
Preferably, the solid content of the nano-silica sol is 15-30%, and the particle size of the nano-titanium oxide is 5-30 nm.
Preferably, the structure directing agent is prepared from cetyl trimethyl ammonium bromide, sodium polyepoxysuccinate according to a ratio of 1: (0.5-3) in mass ratio.
Preferably, the aminosilane coupling agent is one or more of 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, and N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane.
Preferably, the emulsifier is one or more of fatty alcohol-polyoxyethylene ether, sodium lauroyl glutamate and sodium dodecyl benzene sulfonate.
The invention has the beneficial effects that:
1. the first hydrophobic repairing liquid and the etching liquid are combined to process the glass substrate, the etching liquid A and the etching liquid B are adopted to respectively etch, and Ca is used2+、Mg2+After surface modification, surface treatment is carried out by using hydrophobic repair liquid, so that the defect position on the surface of the etched glass substrate is repaired, and the structural stability and the mechanical strength of the ultrathin glass are improved; meanwhile, the hydrophobic repairing liquid endows the glass with flexibility, so that the ultra-thin glass is effectively prevented from being cracked, has the functions of water resistance, hydrophobicity and self-cleaning, and improves the comprehensive performance of the ultra-thin glass.
2. The invention uses Ca firstly2+、Mg2+Surface modifying the etched glass to make the surface defect position enriched with etching Ca2+、Mg2+And then the hydrophobic repairing liquid is utilized to carry out in-situ repair, because the hydrophobic repairing liquid comprises sodium silicate, sodium fluoride, a structure directing agent (polyepoxysuccinic acid sodium) and Ca2+、Mg2+The calcium silicate/magnesium-calcium fluoride/magnesium-polyepoxy succinic acid calcium/magnesium composite crystal is finally formed at the interface junction; meanwhile, due to the chemical crosslinking action of epoxy groups in the polyepoxysuccinic acid sodium salt and hydroxyl groups on the surfaces of sol particles and the hydrogen bonding action of carboxyl groups and hydroxyl groups, nano titanium oxide and nano silicon oxide are stably combined with crystals, the filling and repairing action of the nano titanium oxide and the nano silicon oxide on defect positions is promoted, and the photolysis self-cleaning property, the wear resistance and the high temperature resistance of the ultrathin glass are improved; secondly, the water-based fluorocarbon emulsion and the water repellent agent reduce the surface tension of the glass, so that the ultrathin glass has a lotus leaf hydrophobic effect; in addition, the calcium fluoride and the magnesium fluoride which are generated improve the optical performance of the ultrathin glass and reduce the reflection and the permeability.
3. The invention utilizes hydrophobic repairing liquid and Ca2+、Mg2+The method has the advantages that calcium silicate/magnesium-calcium fluoride/magnesium-polyepoxysuccinic acid calcium/magnesium-nano titanium oxide-nano silicon oxide heterogeneous layers are generated on glass, fluorocarbon film layers are formed, double-side coating is carried out, the ultrathin glass is formed by overlapping five different medium layers, and due to different refractive indexes of the medium layers, when the ultrathin glass is applied to various mobile phone touch screen cover plates, a light source penetrates through the different medium layers to be repeatedly refracted and reflected for multiple times, so that a display screen is more uniformly imaged, the light is uniform in luminescence, and the ultrathin glass has a good anti-dazzle effect.
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FIG. 1 is a flow chart of a method for etching ultra-thin glass according to the present invention;
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1
The method for etching and manufacturing the ultra-thin glass comprises the following steps: miningEtching with etching solution A and etching solution B, respectively, and etching with Ca2+、Mg2 +After surface modification, performing surface treatment by using a hydrophobic repair liquid; the method specifically comprises the following steps:
s1: cleaning: wiping a glass substrate with the thickness of 200 mu m with absolute ethyl alcohol, removing surface grease, washing with clear water for 2 times, and naturally drying;
s2: first etching treatment: soaking the glass substrate cleaned in the S1 in the etching solution A, carrying out ultrasonic treatment at 25 ℃, carrying out etching thinning treatment until the thickness of the glass substrate is 100 mu m, and washing and drying;
the etching solution A takes water as a solvent and comprises the following components in molar concentration: 1.5mol/L hydrofluoric acid, 0.5mol/L hydrochloric acid, 1.0mol/L sodium fluosilicate and 0.1mol/L sodium dodecyl sulfate;
s3: and (3) second etching treatment: placing the glass substrate etched in S2 in an etching tank, etching and thinning the glass substrate to 20 μm by using etching solution B, and washing and drying;
the etching solution B takes water as a solvent and comprises the following components in molar concentration: 0.5mol/L hydrofluoric acid, 0.3mol/L hydrochloric acid, 0.5mol/L sodium fluosilicate and 0.1mol/L sodium dodecyl sulfate;
s4: surface modification: soaking the etched glass substrate of S3 in a solution containing 0.05mol/L CaCl2、0.05mol/L MgCl2The mixed solution is subjected to ultrasonic treatment for 0.5h at 40 ℃, and is dried at 80 ℃ after being taken out;
s5: surface treatment: uniformly coating the hydrophobic repairing liquid on two surfaces of the glass substrate with the modified S4 surface, controlling the coating thickness of one surface to be 1 mu m, and curing and drying at 80 ℃ for 6h to obtain the ultrathin glass;
the hydrophobic repairing liquid comprises the following components in parts by mass: 40 parts of aqueous fluorocarbon emulsion with solid content of 30%, 1 part of tridecafluorooctyltriethoxysilane, 5 parts of sodium silicate, 2 parts of sodium fluoride, 10 parts of solid content, 10 parts of nano titanium oxide sol with the particle size range of 5-20 nm, 15 parts of solid content, 15 parts of nano silicon oxide sol with the particle size range of 5-30 nm, 3 parts of structure directing agent, 1 part of 3-aminopropyltriethoxysilane and 0.5 part of fatty alcohol-polyoxyethylene ether; the structure directing agent is prepared from hexadecyl trimethyl ammonium bromide and polyepoxysuccinic acid sodium according to the weight ratio of 1: 1.5 by mass ratio.
Example 2
The method for etching and manufacturing the ultra-thin glass comprises the following steps: etching with etching solution A and etching solution B, respectively, using Ca2+、Mg2 +After surface modification, performing surface treatment by using a hydrophobic repair liquid; the method specifically comprises the following steps:
s1: cleaning: wiping a glass substrate with the thickness of 300 mu m by absolute ethyl alcohol, removing surface grease, washing for 3 times by using clear water, and naturally drying;
s2: first etching treatment: soaking the glass substrate cleaned in the S1 in the etching solution A, carrying out ultrasonic treatment at 25 ℃, carrying out etching thinning treatment until the thickness of the glass substrate is 125 mu m, and washing and drying;
the etching solution A takes water as a solvent and comprises the following components in molar concentration: 2mol/L hydrofluoric acid, 1mol/L hydrochloric acid, 1.2mol/L sodium fluosilicate and 0.15mol/L sodium dodecyl sulfate;
s3: and (3) second etching treatment: placing the glass substrate etched in S2 in an etching tank, etching and thinning the glass substrate to 25 μm by using etching solution B, and washing and drying;
the etching solution B takes water as a solvent and comprises the following components in molar concentration: 1mol/L hydrofluoric acid, 0.6mol/L hydrochloric acid, 0.6mol/L sodium fluosilicate and 0.15mol/L sodium dodecyl sulfate;
s4: surface modification: soaking the etched glass substrate of S3 in a solution containing 0.1mol/L CaCl2、0.1mol/L MgCl2The mixed solution is subjected to ultrasonic treatment for 1h at 50 ℃, and then is dried at 80 ℃ after being taken out;
s5: surface treatment: uniformly coating the hydrophobic repairing liquid on two surfaces of the glass substrate with the modified S4 surface, controlling the coating thickness of one surface to be 2 microns, and curing and drying at 100 ℃ for 8 hours to obtain the ultrathin glass;
the hydrophobic repairing liquid comprises the following components in parts by mass: 45 parts of aqueous fluorocarbon emulsion with solid content of 35%, 2 parts of heptadecafluorodecyltriethoxysilane, 6 parts of sodium silicate, 2.5 parts of sodium fluoride, 12.5 parts of nano titanium oxide sol with solid content of 5-20 nm, 18 parts of nano silicon oxide sol with solid content of 25% and silicon oxide particle size of 5-30 nm, 4 parts of structure directing agent, 1.5 parts of 3-aminopropylmethyldiethoxysilane and 1 part of sodium lauroyl glutamate; the structure directing agent is prepared from hexadecyl trimethyl ammonium bromide and polyepoxysuccinic acid sodium according to the weight ratio of 1: 2, and mixing the components in a mass ratio.
Example 3
The method for etching and manufacturing the ultra-thin glass comprises the following steps: etching with etching solution A and etching solution B, respectively, using Ca2+、Mg2 +After surface modification, performing surface treatment by using a hydrophobic repair liquid; the method specifically comprises the following steps:
s1: cleaning: wiping a glass substrate with the thickness of 400 mu m by absolute ethyl alcohol, removing surface grease, washing for 3 times by using clear water, and naturally drying;
s2: first etching treatment: soaking the glass substrate cleaned in the S1 in the etching solution A, carrying out ultrasonic treatment at 25 ℃, carrying out etching thinning treatment until the thickness of the glass substrate is 150 mu m, and washing and drying;
the etching solution A takes water as a solvent and comprises the following components in molar concentration: 3mol/L hydrofluoric acid, 1.5mol/L hydrochloric acid, 1.5mol/L sodium fluosilicate and 0.2mol/L sodium dodecyl sulfate;
s3: and (3) second etching treatment: placing the glass substrate etched in S2 in an etching tank, etching and thinning the glass substrate to 30 μm by using etching solution B, and washing and drying;
the etching solution B takes water as a solvent and comprises the following components in molar concentration: 1.5mol/L hydrofluoric acid, 0.8mol/L hydrochloric acid, 0.8mol/L sodium fluosilicate and 0.2mol/L sodium dodecyl sulfate;
s4: surface modification: soaking the etched glass substrate of S3 in a solution containing 0.2mol/L CaCl2、0.2mol/L MgCl2The mixed solution is subjected to ultrasonic treatment for 1h at the temperature of 60 ℃, and is dried at the temperature of 80 ℃ after being taken out;
s5: surface treatment: uniformly coating the hydrophobic repairing liquid on two surfaces of the glass substrate with the modified S4 surface, controlling the coating thickness of one surface to be 4 microns, and curing and drying at 120 ℃ for 10 hours to obtain the ultrathin glass;
the hydrophobic repairing liquid comprises the following components in parts by mass: 50 parts of aqueous fluorocarbon emulsion with solid content of 40%, 3 parts of trifluoropropylmethyl silicone oil, 7 parts of sodium silicate, 3 parts of sodium fluoride, 15 parts of nano-titanium oxide sol with solid content of 15%, the particle size range of titanium oxide of 5-20 nm, 20 parts of nano-silicon oxide sol with solid content of 30%, the particle size range of silicon oxide of 5-30 nm, 5 parts of structure directing agent, 2 parts of N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and 2 parts of sodium dodecyl benzene sulfonate; the structure directing agent is prepared from hexadecyl trimethyl ammonium bromide and polyepoxysuccinic acid sodium according to the weight ratio of 1: 3, and the components are mixed according to the mass ratio.
Comparative example 1 is the same as example 1 except that: no S4 Ca2+、Mg2+And (5) performing surface modification operation.
Comparative example 2 is the same as example 1 except that: and the surface treatment operation of the hydrophobic repair liquid is not S5.
Comparative example 3 is the same as example 1 except that: the hydrophobic repair liquid of S5 does not contain nano titanium oxide sol and nano silicon oxide sol.
Comparative example 4 is the same as example 1 except that: the hydrophobic repair liquid of S5 does not contain a structure directing agent.
The performance of the ultra-thin glass manufactured in examples 1 to 3 and comparative examples 1 to 4 was tested, and the test results are shown in the following table:
as can be seen from the table above, the ultrathin glass prepared by the method is rigid and flexible, has good hardness and toughness, high light transmittance, hydrophobic property, stain resistance, glare resistance and excellent comprehensive performance.
Examples 1-3 first treating a glass substrate with a hydrophobic repairing solution in combination with an etching solution, etching the glass substrate with an etching solution A and an etching solution B, respectively, using Ca2+、Mg2+After surface modification, the surface is treated by hydrophobic repairing liquidProcessing, namely repairing the surface defect position of the etched glass substrate, and improving the structural stability and mechanical strength of the ultrathin glass; meanwhile, the hydrophobic repairing liquid endows the glass with flexibility, so that the ultra-thin glass is effectively prevented from being cracked, has the functions of water resistance, hydrophobicity and self-cleaning, and improves the comprehensive performance of the ultra-thin glass.
Examples 1 to 3 use Ca first2+、Mg2+Surface modifying the etched glass to make the surface defect position enriched with etching Ca2+、Mg2+And then the hydrophobic repairing liquid is utilized to carry out in-situ repair, because the hydrophobic repairing liquid comprises sodium silicate, sodium fluoride, a structure directing agent (polyepoxysuccinic acid sodium) and Ca2+、Mg2+The calcium silicate/magnesium-calcium fluoride/magnesium-polyepoxy succinic acid calcium/magnesium composite crystal is finally formed at the interface junction; meanwhile, due to the chemical crosslinking action of epoxy groups in the polyepoxysuccinic acid sodium salt and hydroxyl groups on the surfaces of sol particles and the hydrogen bonding action of carboxyl groups and hydroxyl groups, nano titanium oxide and nano silicon oxide are stably combined with crystals, the filling and repairing action of the nano titanium oxide and the nano silicon oxide on defect positions is promoted, and the photolysis self-cleaning property, the wear resistance and the high temperature resistance of the ultrathin glass are improved; secondly, the water-based fluorocarbon emulsion and the water repellent agent reduce the surface tension of the glass, so that the ultrathin glass has a lotus leaf hydrophobic effect; in addition, the optical performance of the ultrathin glass is improved due to the calcium fluoride and the magnesium fluoride.
Examples 1-3 use of hydrophobic remediation solution with Ca2+、Mg2+The method has the advantages that calcium silicate/magnesium-calcium fluoride/magnesium-polyepoxysuccinic acid calcium/magnesium-nano titanium oxide-nano silicon oxide heterogeneous layers are generated on glass, fluorocarbon film layers are formed, double-side coating is carried out, the ultrathin glass is formed by overlapping five different medium layers, and due to different refractive indexes of the medium layers, when the ultrathin glass is applied to various mobile phone touch screen cover plates, a light source penetrates through the different medium layers to be repeatedly refracted and reflected for multiple times, so that a display screen is more uniformly imaged, the light is uniform in luminescence, and the ultrathin glass has a good anti-dazzle effect.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (8)
1. A method for etching ultra-thin glass, characterized by: etching with etching solution A and etching solution B, respectively, using Ca2+、Mg2+After surface modification, performing surface treatment by using a hydrophobic repair liquid;
the etching solution A takes water as a solvent and comprises the following components in molar concentration: 1.5-3 mol/L hydrofluoric acid, 0.5-1.5 mol/L hydrochloric acid, 1.0-1.5 mol/L sodium fluosilicate and 0.1-0.2 mol/L sodium dodecyl sulfate;
the etching solution B takes water as a solvent and comprises the following components in molar concentration: 0.5-1.5 mol/L hydrofluoric acid, 0.3-0.8 mol/L hydrochloric acid, 0.5-0.8 mol/L sodium fluosilicate and 0.1-0.2 mol/L sodium dodecyl sulfate;
the hydrophobic repairing liquid comprises the following components in parts by mass: 40-50 parts of water-based fluorocarbon emulsion, 1-3 parts of hydrophobic agent, 5-7 parts of sodium silicate, 2-3 parts of sodium fluoride, 10-15 parts of nano titanium oxide sol, 15-20 parts of nano silicon oxide sol, 3-5 parts of structure directing agent, 1-2 parts of aminosilane coupling agent and 0.5-2 parts of emulsifier;
the method specifically comprises the following steps:
s1: cleaning: wiping a glass substrate with the thickness of 200-400 mu m with absolute ethyl alcohol, removing surface grease, washing with clear water for 2-3 times, and naturally drying;
s2: first etching treatment: soaking the glass substrate cleaned in the S1 in the etching solution A, carrying out ultrasonic treatment at 25 ℃, carrying out etching thinning treatment until the thickness of the glass substrate is 100-150 mu m, and washing and drying;
s3: and (3) second etching treatment: placing the glass substrate etched in S2 in an etching tank, etching and thinning the glass substrate to 20-30 μm in thickness by using etching solution B, and washing and drying;
s4: surface modification: immersing the etched glass substrate of S3 in a solution containing 0.05-0.2 mol/LCaCl2、0.05～0.2mol/LMgCl2Carrying out ultrasonic treatment for 0.5-1 h at 40-60 ℃, taking out, and drying at 80 ℃;
s5: surface treatment: and (3) uniformly coating the hydrophobic repairing liquid on the surface of the glass substrate modified by the S4 surface, controlling the thickness of the single-side coating to be 0.5-4 mu m, and curing and drying at 60-120 ℃ for 6-10 h to obtain the ultrathin glass.
2. The method for etching ultrathin glass according to claim 1, wherein the solid content of the aqueous fluorocarbon emulsion is 30-40%.
3. The method for etching ultrathin glass as claimed in claim 1, wherein the hydrophobic agent is one or more of tridecafluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane, octamethylcyclotetrasiloxane, trifluoropropylmethylsilicone oil.
4. The method for etching an ultra-thin glass as claimed in claim 1, wherein the nano titania sol has a solid content of 10 to 15% and a particle size of 5 to 20 nm.
5. The method for etching an ultra-thin glass as claimed in claim 1, wherein the nano silica sol has a solid content of 15 to 30% and the nano titania has a particle size of 5 to 30 nm.
6. The method for etching ultrathin glasses according to claim 1, wherein the structure directing agent is a mixture of cetyltrimethylammonium bromide, sodium polyepoxysuccinate in a ratio of 1: (0.5-3) in mass ratio.
7. The method for etching ultrathin glass as claimed in claim 1, wherein the aminosilane coupling agent is one or more of 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane.
8. The method for etching ultrathin glass according to claim 1, wherein the emulsifier is one or more of fatty alcohol-polyoxyethylene ether, sodium lauroyl glutamate and sodium dodecyl benzene sulfonate.
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| CN115490433A (en) * | 2022-09-30 | 2022-12-20 | 海南海控特玻科技有限公司 | Anti-reflection high-aluminosilicate glass and preparation method thereof |
| CN115784623A (en) * | 2022-11-18 | 2023-03-14 | 江西沃格光电股份有限公司 | Glass thinning pretreatment liquid, glass thinning method and application thereof |
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