CN112551909B - Method for etching to make ultra-thin glass - Google Patents

Method for etching to make ultra-thin glass Download PDF

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Publication number
CN112551909B
CN112551909B CN202011454116.4A CN202011454116A CN112551909B CN 112551909 B CN112551909 B CN 112551909B CN 202011454116 A CN202011454116 A CN 202011454116A CN 112551909 B CN112551909 B CN 112551909B
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etching
parts
sodium
glass substrate
hydrophobic
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CN112551909A (en
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倪植森
张少波
陈诚
杨金发
彭程
许波
钟汝梅
李俊琛
邵帅
罗丹
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Bengbu Huayi Branch Of Kaisheng Technology Co ltd
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    • 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
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • 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
    • 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
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

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  • 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)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

The present invention discloses a method for etching manufactureThe method for ultrathin glass comprises the following steps: etching with etching solution A and etching solution B, respectively, using Ca 2+ 、Mg 2+ After surface modification, carrying out 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 to 3mol/L of hydrofluoric acid, 0.5 to 1.5mol/L of hydrochloric acid, 1.0 to 1.5mol/L of sodium fluosilicate and 0.1 to 0.2mol/L of sodium dodecyl sulfate; the etching solution B takes water as a solvent and comprises the following components in molar concentration: 0.5 to 1.5mol/L hydrofluoric acid, 0.3 to 0.8mol/L hydrochloric acid, 0.5 to 0.8mol/L sodium fluosilicate and 0.1 to 0.2mol/L sodium dodecyl sulfate; the hydrophobic repair 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, 15-20 parts of nano silica sol, 3-5 parts of structure directing agent, 1-2 parts of amino silane coupling 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; and the glass is endowed with flexibility, so that the ultrathin glass is prevented from being broken.

Description

Method for etching to make ultra-thin glass
Technical Field
The invention belongs to the technical field of glass etching, and particularly relates to a method for etching and manufacturing ultrathin glass.
Background
Ultrathin glass is a representation of the trend of globalized consumer electronics toward lighter and thinner products, and is also gradually developing toward more ultrathin products in the aspects of smart phones and notebook computers. With the maturity of related software and hardware industry and higher requirements on thinning application, ultra-thin glass is widely applied to mobile phone cover plates.
Because the ultrathin glass is mainly subjected to chemical etching and thinning by adopting hydrofluoric acid, the original defects on the surface of the glass are further exposed and amplified, so that the stress distribution on the surface of the glass is uneven, when the glass is used for a mobile phone touch screen cover plate, the compressive strength and toughness of a glass substrate are weakened, the problem that broken screens are broken easily occurs, and broken screens are the most common problems in the use process of the smart phone.
Based on the above, the present invention discloses a method for etching and manufacturing ultra-thin glass to produce ultra-thin glass which satisfies both light weight, thin and thin, high compressive strength and toughness, and is not fragile.
Disclosure of Invention
In view of the shortcomings of the prior art, it is an object of the present invention to provide a method for etching to make ultra-thin glass.
The technical scheme of the invention is summarized as follows:
a method for etching to make ultra-thin glass: etching with etching solution A and etching solution B, respectively, using Ca 2+ 、Mg 2 + After surface modification, carrying out 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 to 3mol/L of hydrofluoric acid, 0.5 to 1.5mol/L of hydrochloric acid, 1.0 to 1.5mol/L of sodium fluosilicate and 0.1 to 0.2mol/L of sodium dodecyl sulfate;
the etching solution B takes water as a solvent and comprises the following components in molar concentration: 0.5 to 1.5mol/L hydrofluoric acid, 0.3 to 0.8mol/L hydrochloric acid, 0.5 to 0.8mol/L sodium fluosilicate and 0.1 to 0.2mol/L sodium dodecyl sulfate;
the hydrophobic repair 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, 15-20 parts of nano silica sol, 3-5 parts of structure directing agent, 1-2 parts of aminosilane coupling agent and 0.5-2 parts of emulsifying agent;
the method specifically comprises the following steps:
s1: cleaning: wiping a glass substrate with the thickness of 200-400 mu m by using absolute ethyl alcohol, removing surface grease, washing for 2-3 times by using clear water, and naturally air-drying;
s2: first etching treatment: immersing the glass substrate after S1 cleaning in etching solution A, carrying out ultrasonic treatment at 25 ℃, etching and thinning until the thickness of the glass substrate is 100-150 mu m, and washing and drying;
s3: and (3) performing second etching treatment: placing the glass substrate after S2 etching into an etching groove, etching and thinning the glass substrate by etching solution B until the thickness of the glass substrate is 20-30 mu m, and washing and drying the glass substrate;
s4: surface modification: immersing the glass substrate after S3 etching in a solution containing 0.05-0.2 mol/L CaCl 2 、0.05～0.2mol/L MgCl 2 In the mixed solution of (2), ultrasonic treatment is carried out for 0.5 to 1 hour at the temperature of 40 to 60 ℃, and the mixed solution is dried at the temperature of 80 ℃ after being taken out;
s5: surface treatment: and uniformly coating the hydrophobic repair liquid on the surface of the glass substrate after the S4 surface modification, controlling the single-sided coating thickness to be 0.5-4 mu m, and curing and drying at 60-120 ℃ for 6-10 hours 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, octamethyl cyclotetrasiloxane and trifluoropropyl methyl silicone oil.
Preferably, the solid content of the nano titanium oxide sol is 10-15%, and the particle size range 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 range 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 1: (0.5-3) and mixing the components according to the mass ratio.
Preferably, the aminosilane coupling agent is one or more of 3-aminopropyl triethoxysilane, 3-aminopropyl methyldiethoxysilane, and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane.
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 invention combines the first hydrophobic repair liquid and the etching liquid to treat the glass substrate, adopts the etching liquid A and the etching liquid B to respectively etch, uses Ca 2+ 、Mg 2+ After the surface is modified, the surface treatment is carried out by using a hydrophobic repair liquid, so that the repair of the surface defect position of the etched glass substrate is realized, and the structural stability and the mechanical strength of the ultrathin glass are improved; meanwhile, the hydrophobic repair liquid endows the glass with flexibility, so that the occurrence of fragmentation of the ultrathin glass is effectively prevented, the ultrathin glass has the functions of water resistance, hydrophobicity and self-cleaning, and the comprehensive performance of the ultrathin glass is improved.
2. The invention uses Ca first 2+ 、Mg 2+ Surface modifying etched glass to enrich and etch Ca in surface defect positions 2+ 、Mg 2+ Then the hydrophobic repair liquid is used for in-situ repair, and the hydrophobic repair liquid sodium silicate, sodium fluoride, structure directing agent (polyepoxysuccinate sodium) and Ca are used for in-situ repair 2+ 、Mg 2+ At the interface junction, finally forming calcium/magnesium silicate-calcium fluoride/magnesium-polyepoxysuccinate calcium/magnesium composite crystals; meanwhile, due to the chemical crosslinking action of epoxy groups in the sodium polyepoxysuccinate and hydroxyl groups on the surfaces of sol particles and the hydrogen bonding action of carboxyl groups and hydroxyl groups, the nano titanium oxide and the nano silicon oxide are combined with crystals stably, the filling and repairing action of the nano titanium oxide and the nano silicon oxide on defect positions is improved, and the photodecomposition self-cleaning performance, the wear resistance and the high temperature resistance of the ultrathin glass are improved; secondly, the surface tension of the glass is reduced by the water-based fluorocarbon emulsion and the hydrophobic agent, so that the ultrathin glass presents a lotus leaf hydrophobic effect; in addition, the products of calcium fluoride and magnesium fluoride improve the optical performance of the ultrathin glass, and the reflection are reduced.
3. The invention utilizes the hydrophobic repair liquid and Ca 2+ 、Mg 2+ The glass is used for generating a calcium silicate/magnesium-calcium fluoride/magnesium-polyepoxysuccinate/magnesium-nano titanium oxide-nano silicon oxide heterogeneous layer, then a fluorocarbon film layer is formed, and the glass is coated on two sides, which is equivalent to ultra-thin glass which is formed by laminating five layers of different medium layers.
Drawings
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 described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
Example 1
A method for etching to make ultra-thin glass: etching with etching solution A and etching solution B, respectively, using Ca 2+ 、Mg 2 + After surface modification, carrying out 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 by using absolute ethyl alcohol, removing surface grease, washing for 2 times by using clear water, and naturally air-drying;
s2: first etching treatment: immersing the glass substrate after S1 cleaning in an etching solution A, carrying out ultrasonic treatment at 25 ℃, etching and thinning 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) performing second etching treatment: placing the glass substrate after S2 etching into an etching groove, etching and thinning the glass substrate by etching solution B until the thickness of the glass substrate is 20 mu m, and washing and drying the glass substrate;
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: immersing the glass substrate after S3 etching in a solution containing 0.05mol/L CaCl 2 、0.05mol/L MgCl 2 In the mixed solution of (2), ultrasonic treatment is carried out for 0.5h at 40 ℃, and the mixed solution is dried at 80 ℃ after being taken out;
s5: surface treatment: uniformly coating the hydrophobic repair liquid on two sides of the glass substrate subjected to S4 surface modification, controlling the single-sided coating thickness to be 1 mu m, and curing and drying at 80 ℃ for 6 hours to obtain the ultrathin glass;
the hydrophobic repair liquid comprises the following components in parts by mass: 40 parts of aqueous fluorocarbon emulsion with 30 percent of solid content, 1 part of tridecafluorooctyl triethoxysilane, 5 parts of sodium silicate, 2 parts of sodium fluoride, 10 parts of nano titanium oxide sol with 10 percent of solid content, 10 parts of nano titanium oxide sol with 5-20 nm of titanium oxide particle size, 15 parts of nano silicon oxide sol with 15 percent of solid content and 5-30 nm of silicon oxide particle size, 3 parts of structure directing agent, 1 part of 3-aminopropyl triethoxysilane and 0.5 part of fatty alcohol polyoxyethylene ether; the structure directing agent is prepared from hexadecyl trimethyl ammonium bromide and polyepoxysuccinate sodium according to the following ratio of 1:1.5 mass ratio.
Example 2
A method for etching to make ultra-thin glass: etching with etching solution A and etching solution B, respectively, using Ca 2+ 、Mg 2 + After surface modification, carrying out 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 using absolute ethyl alcohol, removing surface grease, washing for 3 times by using clear water, and naturally air-drying;
s2: first etching treatment: immersing the glass substrate after S1 cleaning in etching solution A, carrying out ultrasonic treatment at 25 ℃, etching and 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: hydrofluoric acid 2mol/L, hydrochloric acid 1mol/L, sodium fluosilicate 1.2mol/L and sodium dodecyl sulfate 0.15mol/L;
s3: and (3) performing second etching treatment: placing the glass substrate after S2 etching into an etching groove, etching and thinning the glass substrate by etching solution B until the thickness of the glass substrate is 25 mu m, and washing and drying the glass substrate;
the etching solution B takes water as a solvent and comprises the following components in molar concentration: 1mol/L of hydrofluoric acid, 0.6mol/L of hydrochloric acid, 0.6mol/L of sodium fluosilicate and 0.15mol/L of sodium dodecyl sulfate;
s4: surface modification: immersing the glass substrate after S3 etching in a solution containing 0.1mol/L CaCl 2 、0.1mol/L MgCl 2 In the mixed solution of (2), carrying out ultrasonic treatment at 50 ℃ for 1h, taking out, and drying at 80 ℃;
s5: surface treatment: uniformly coating the hydrophobic repair liquid on two sides of the glass substrate after S4 surface modification, controlling the single-sided coating thickness to be 2 mu m, and curing and drying at 100 ℃ for 8 hours to obtain the ultrathin glass;
the hydrophobic repair liquid comprises the following components in parts by mass: 45 parts of aqueous fluorocarbon emulsion with the solid content of 35 percent, 2 parts of heptadecafluorodecyl triethoxysilane, 6 parts of sodium silicate, 2.5 parts of sodium fluoride, 12 parts of nano titanium oxide sol with the solid content of 12.5 percent and the titanium oxide particle size range of 5-20 nm, 18 parts of nano silicon oxide sol with the solid content of 25 percent and the silicon oxide particle size range of 5-30 nm, 4 parts of structure directing agent, 1.5 parts of 3-aminopropyl methyl diethoxy silane and 1 part of sodium lauroyl glutamate; the structure directing agent is prepared from hexadecyl trimethyl ammonium bromide and polyepoxysuccinate sodium according to the following ratio of 1:2 mass ratio.
Example 3
A method for etching to make ultra-thin glass: etching with etching solution A and etching solution B, respectively, using Ca 2+ 、Mg 2 + After surface modification, carrying out 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 using absolute ethyl alcohol, removing surface grease, washing for 3 times by using clear water, and naturally air-drying;
s2: first etching treatment: immersing the glass substrate after S1 cleaning in an etching solution A, carrying out ultrasonic treatment at 25 ℃, etching and thinning 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 of hydrofluoric acid, 1.5mol/L of hydrochloric acid, 1.5mol/L of sodium fluosilicate and 0.2mol/L of sodium dodecyl sulfate;
s3: and (3) performing second etching treatment: placing the glass substrate after S2 etching into an etching groove, etching and thinning the glass substrate by etching solution B until the thickness of the glass substrate is 30 mu m, and washing and drying the glass substrate;
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: immersing the glass substrate after S3 etching in a solution containing 0.2mol/L CaCl 2 、0.2mol/L MgCl 2 In the mixed solution of (2), ultrasonic treatment is carried out for 1h at 60 ℃, and the mixed solution is dried at 80 ℃ after being taken out;
s5: surface treatment: uniformly coating the hydrophobic repair liquid on two sides of the glass substrate subjected to S4 surface modification, controlling the single-sided coating thickness to be 4 mu m, and curing and drying at 120 ℃ for 10 hours to obtain the ultrathin glass;
the hydrophobic repair liquid comprises the following components in parts by mass: 50 parts of aqueous fluorocarbon emulsion with the solid content of 40 percent, 3 parts of trifluoropropyl methyl silicone oil, 7 parts of sodium silicate, 3 parts of sodium fluoride, 15 parts of nano titanium oxide sol with the solid content of 15 percent, the titanium oxide particle size range of 5-20 nm, 20 parts of nano silicon oxide sol with the solid content of 30 percent and the silicon oxide particle size range of 5-30 nm, 5 parts of structure directing agent, 2 parts of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane and 2 parts of sodium dodecyl benzene sulfonate; the structure directing agent is prepared from hexadecyl trimethyl ammonium bromide and polyepoxysuccinate sodium according to the following ratio of 1:3 mass ratio.
Comparative example 1 is the same as example 1, except that: s4 Ca free 2+ 、Mg 2+ Surface modification operation.
Comparative example 2 is the same as example 1, except that: and S5, the surface treatment operation of the hydrophobic repair liquid is avoided.
Comparative example 3 is the same as example 1, except that: s5, the hydrophobic repair liquid does not contain nano titanium oxide sol and nano silica sol.
Comparative example 4 is the same as example 1, except that: s5, the hydrophobic repair liquid does not contain a structure directing agent.
The ultra-thin glasses produced in examples 1 to 3 and comparative examples 1 to 4 were subjected to performance tests, and the test results are shown in the following table:
as shown in the table, the ultrathin glass manufactured by the method is rigid and flexible, has better hardness and toughness, high light transmittance, is hydrophobic and anti-fouling, can prevent glare, and has excellent comprehensive performance.
Examples 1 to 3 first hydrophobic repair liquid and etching liquid were combined to treat glass substrates, etching was performed with etching liquid A and etching liquid B, respectively, using Ca 2+ 、Mg 2+ After the surface is modified, the surface treatment is carried out by using a hydrophobic repair liquid, so that the repair of the surface defect position of the etched glass substrate is realized, and the structural stability and the mechanical strength of the ultrathin glass are improved; meanwhile, the hydrophobic repair liquid endows the glass with flexibility, so that the occurrence of fragmentation of the ultrathin glass is effectively prevented, the ultrathin glass has the functions of water resistance, hydrophobicity and self-cleaning, and the comprehensive performance of the ultrathin glass is improved.
EXAMPLES 1 to 3 Ca was used first 2+ 、Mg 2+ Surface modifying etched glass to enrich and etch Ca in surface defect positions 2+ 、Mg 2+ Then the hydrophobic repair liquid is used for in-situ repair, and the hydrophobic repair liquid sodium silicate, sodium fluoride, structure directing agent (polyepoxysuccinate sodium) and Ca are used for in-situ repair 2+ 、Mg 2+ At the interface junction, finally forming calcium/magnesium silicate-calcium fluoride/magnesium-polyepoxysuccinate calcium/magnesium composite crystals; meanwhile, due to the chemical crosslinking action of epoxy groups in the polyepoxysuccinic acid sodium salt and the surface hydroxyl groups of sol particles and the hydrogen bonding action of carboxyl groups and hydroxyl groups, the nano titanium oxide and the nano silicon oxide are stably combined with crystals, and the nano is promotedThe titanium oxide and the nano silicon oxide have the filling and repairing effects on the defect positions, so that the photodecomposition self-cleaning performance, the wear resistance and the high temperature resistance of the ultrathin glass are improved; secondly, the surface tension of the glass is reduced by the water-based fluorocarbon emulsion and the hydrophobic agent, so that the ultrathin glass presents a lotus leaf hydrophobic effect; in addition, the optical properties of the ultrathin glass are improved due to the products of calcium fluoride and magnesium fluoride.
Examples 1 to 3 use of a hydrophobic repair liquid with Ca 2+ 、Mg 2+ The glass is used for generating a calcium silicate/magnesium-calcium fluoride/magnesium-polyepoxysuccinate/magnesium-nano titanium oxide-nano silicon oxide heterogeneous layer, then a fluorocarbon film layer is formed, and the glass is coated on two sides, which is equivalent to ultra-thin glass which is formed by laminating five layers of different medium layers.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.

Claims (7)

1. A method for etching to make ultra-thin glass, characterized by: etching with etching solution A and etching solution B, respectively, using Ca 2+ 、Mg 2+ After surface modification, carrying out 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 to 3mol/L of hydrofluoric acid, 0.5 to 1.5mol/L of hydrochloric acid, 1.0 to 1.5mol/L of sodium fluosilicate and 0.1 to 0.2mol/L of sodium dodecyl sulfate;
the etching solution B takes water as a solvent and comprises the following components in molar concentration: 0.5 to 1.5mol/L hydrofluoric acid, 0.3 to 0.8mol/L hydrochloric acid, 0.5 to 0.8mol/L sodium fluosilicate and 0.1 to 0.2mol/L sodium dodecyl sulfate;
the hydrophobic repair 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, 15-20 parts of nano silica sol, 3-5 parts of structure directing agent, 1-2 parts of aminosilane coupling agent and 0.5-2 parts of emulsifying agent;
the method specifically comprises the following steps:
s1: cleaning: wiping a glass substrate with the thickness of 200-400 mu m by using absolute ethyl alcohol, removing surface grease, washing for 2-3 times by using clear water, and naturally air-drying;
s2: first etching treatment: immersing the glass substrate after S1 cleaning in etching solution A, carrying out ultrasonic treatment at 25 ℃, etching and thinning until the thickness of the glass substrate is 100-150 mu m, and washing and drying;
s3: and (3) performing second etching treatment: placing the glass substrate after S2 etching into an etching groove, etching and thinning the glass substrate by etching solution B until the thickness of the glass substrate is 20-30 mu m, and washing and drying the glass substrate;
s4: surface modification: immersing the glass substrate after S3 etching in a solution containing 0.05-0.2 mol/LCaCl 2 、0.05～0.2mol/LMgCl 2 In the mixed solution of (2), ultrasonic treatment is carried out for 0.5 to 1 hour at the temperature of 40 to 60 ℃, and the mixed solution is dried at the temperature of 80 ℃ after being taken out;
s5: surface treatment: uniformly coating the hydrophobic repair liquid on the surface of the glass substrate after S4 surface modification, controlling the single-sided coating thickness to be 0.5-4 mu m, and curing and drying at 60-120 ℃ for 6-10 hours to obtain the ultrathin glass;
the structure directing agent is prepared from hexadecyl trimethyl ammonium bromide and polyepoxysuccinate sodium according to the following ratio of 1: (0.5-3) and mixing the components according to the mass ratio.
2. The method for etching ultra-thin glass according to claim 1, wherein the aqueous fluorocarbon emulsion has a solids content of 30 to 40%.
3. The method for etching an ultra-thin glass according to claim 1, wherein the hydrophobizing agent is one or more of tridecafluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane, octamethyl cyclotetrasiloxane, trifluoropropyl methyl silicone oil.
4. The method for etching ultra-thin glass according to claim 1, wherein the solid content of the nano titania sol is 10 to 15% and the particle size of the nano titania is 5 to 20nm.
5. The method for etching ultra-thin glass according to claim 1, wherein the solid content of the nano silica sol is 15-30% and the particle size of the nano titania is 5-30 nm.
6. The method for etching ultra-thin glass according to claim 1, wherein the aminosilane coupling agent is one or more of 3-aminopropyl triethoxysilane, 3-aminopropyl methyldiethoxysilane, N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane.
7. The method for etching ultra-thin glass according to claim 1, wherein the emulsifier is one or more of fatty alcohol polyoxyethylene ether, sodium lauroyl glutamate, sodium dodecyl benzene sulfonate.
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