Search

CN-116589191-B - Coated glass ceramics with fluorine polymer hydrophobic and oleophobic layer and preparation method and application thereof

CN116589191BCN 116589191 BCN116589191 BCN 116589191BCN-116589191-B

Abstract

The invention relates to coated glass ceramics with a fluorine polymer hydrophobic and oleophobic layer, a preparation method and application thereof, wherein the coated glass is glass ceramics or glass ceramics with a hydrophobic and oleophobic composite coating on the surface, and the coated glass is characterized by comprising a hydrophobic and oleophobic layer, an intermediate layer, a priming layer and glass ceramics or glass ceramics from the outermost surface of the glass, wherein the intermediate layer is an intermediate layer formed by ionic crystals with lattice energy of 700-3000kJ/mol, and the priming layer comprises a compound or mixed silicon oxide layer containing Si-O bonds. The invention can form a firm, durable and excellent hydrophobic and oleophobic coating on the coating interface of the microcrystalline glass even with a few Si-O structures, and can realize excellent hydrophobic and oleophobic properties no matter whether the high-crystallinity glass is subjected to ion exchange or not.

Inventors

  • HU WEI
  • ZHENG QIFANG
  • HUANG HAO
  • DENG SHUANG
  • TAN BAOQUAN
  • JIANG HONG

Assignees

  • 重庆鑫景特种玻璃有限公司

Dates

Publication Date
20260505
Application Date
20210129

Claims (20)

  1. 1. The microcrystalline glass with the surface containing the hydrophobic and oleophobic composite coating is characterized by sequentially comprising a hydrophobic and oleophobic layer, an intermediate layer and a priming layer from the outermost surface of the microcrystalline glass, wherein the intermediate layer is an ionic crystal with the lattice energy of 725-3000kJ/mol or a fluoride intermediate layer formed by taking a compound with the lattice energy of 9400-11400kJ/mol as an original coating substance, the intermediate layer contains an alkali fluoride metal compound or an alkaline earth fluoride compound or is a fluoride intermediate layer formed by taking an ionic crystal selected from alkali fluoride and alkaline earth fluoride as an original coating substance, the priming layer comprises a compound containing Si-O bonds or a mixed silicon oxide layer, the thickness of the intermediate layer is 1-5nm, and the thickness of the priming layer is 3-15nm; The hydrophobic and oleophobic layer is a fluorine polymer layer, and the thickness of the hydrophobic and oleophobic layer is 10nm-25nm.
  2. 2. The glass-ceramic of claim 1, comprising a coloring additive.
  3. 3. The glass ceramic according to claim 1, wherein the intermediate layer is an intermediate layer formed by taking an ion crystal with a lattice energy of 770-3000kJ/mol as an original coating substance.
  4. 4. The glass ceramic according to claim 2, wherein the intermediate layer is an intermediate layer formed by taking an ion crystal with a lattice energy of 770-3000kJ/mol as an original coating substance.
  5. 5. The glass-ceramic of claim 1, wherein the interlayer is an ion crystal interlayer having a lattice energy of less than 1050 KJ/mol.
  6. 6. The glass-ceramic of claim 1, wherein the interlayer is an ion crystal interlayer having a lattice energy of less than 940 kJ/mol.
  7. 7. The glass ceramic according to claim 1, wherein the interlayer is a crystal formed by using at least one ion crystal of LiF, naF and/or KF as an original coating substance, or an interlayer formed by using at least one of MgF 2 、CaF 2 、SrF 2 or BaF 2 as an original coating substance, or a fluoride interlayer formed by using at least one of Li 2 SiF 6 、Na 2 SiF 6 、K 2 SiF 6 、Rb 2 SiF 6 、Cs 2 SiF 6 、BeSiF 6 、MgSiF 6 、CaSiF 6 、SrSiF 6 、 or BaSiF 6 as an original coating substance.
  8. 8. The glass ceramic according to claim 1, wherein the interlayer is formed by using NaF or KF ion crystals as original coating substances.
  9. 9. The glass-ceramic according to any one of claims 1 to 8, wherein the thickness of the intermediate layer is 1 to 2nm.
  10. 10. The glass ceramic according to any one of claims 1 to 8, wherein the primer layer has a thickness of 5 to 10nm.
  11. 11. The glass ceramic according to any one of claims 1 to 8, wherein the primer layer has a thickness of 5 to 8nm.
  12. 12. Glass-ceramic according to any one of claims 1 to 8, wherein, in the case of a multilayer underlayer, the Si-O bond containing compound or mixed silicon oxide layer is the outermost underlayer, the mixed silicon oxide being a mixture of silicon oxide SiO x and at least one oxide of an element other than silicon element and/or magnesium fluoride, where x is less than or equal to 2.
  13. 13. The glass-ceramic of claim 12, wherein the other element is an element of aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc, or boron.
  14. 14. The glass-ceramic of claim 12, wherein the mixed silicon oxide is a mixture of silicon oxide SiO x and aluminum oxide.
  15. 15. The glass-ceramic according to claim 12, wherein the Si-O bond-containing compound is SiOx, wherein x is 2 or less, or is any one of SiOC, siON and/or SiOCN.
  16. 16. Glass-ceramic according to any one of claims 1 to 8, comprising the following oxides in mol%: SiO 2 :40-75%; Al 2 O 3 :2-20%; B 2 O 3 :0-20%; P 2 O 5 :0-10%; ZrO 2 +TiO 2 :0-15%; MgO:0-5%; ZnO:0-4%; 0-5% of rare earth oxide; Na 2 O:0-5.5%; K 2 O:0-4%; li 2 O2-34%, and Na 2 O+K 2 O+Li 2 O:4-40%。
  17. 17. The glass-ceramic according to claim 12, comprising the following oxides in mole percent: SiO 2 :40-75%; Al 2 O 3 :2-20%; B 2 O 3 :0-20%; P 2 O 5 :0-10%; ZrO 2 +TiO 2 :0-15%; MgO:0-5%; ZnO:0-4%; 0-5% of rare earth oxide; Na 2 O:0-5.5%; K 2 O:0-4%; li 2 O2-34%, and Na 2 O+K 2 O+Li 2 O:4-40%。
  18. 18. The glass-ceramic according to claim 13, comprising the following oxides in mole percent: SiO 2 :40-75%; Al 2 O 3 :2-20%; B 2 O 3 :0-20%; P 2 O 5 :0-10%; ZrO 2 +TiO 2 :0-15%; MgO:0-5%; ZnO:0-4%; 0-5% of rare earth oxide; Na 2 O:0-5.5%; K 2 O:0-4%; li 2 O2-34%, and Na 2 O+K 2 O+Li 2 O:4-40%。
  19. 19. The glass-ceramic according to claim 14, comprising the following oxides in mole percent: SiO 2 :40-75%; Al 2 O 3 :2-20%; B 2 O 3 :0-20%; P 2 O 5 :0-10%; ZrO 2 +TiO 2 :0-15%; MgO:0-5%; ZnO:0-4%; 0-5% of rare earth oxide; Na 2 O:0-5.5%; K 2 O:0-4%; li 2 O2-34%, and Na 2 O+K 2 O+Li 2 O:4-40%。
  20. 20. The glass-ceramic according to claim 15, comprising the following oxides in mole percent: SiO 2 :40-75%; Al 2 O 3 :2-20%; B 2 O 3 :0-20%; P 2 O 5 :0-10%; ZrO 2 +TiO 2 :0-15%; MgO:0-5%; ZnO:0-4%; 0-5% of rare earth oxide; Na 2 O:0-5.5%; K 2 O:0-4%; li 2 O2-34%, and Na 2 O+K 2 O+Li 2 O:4-40%。

Description

Coated glass ceramics with fluorine polymer hydrophobic and oleophobic layer and preparation method and application thereof The application relates to coated microcrystalline glass with increased hydrophobicity and oleophobicity, which is a divisional application of China patent application with application number of 202110128889.1 and application date of 2021, 01 and 29. Technical Field The invention relates to coated glass with hydrophobic and oleophobic properties, a preparation method and application thereof, in particular to microcrystalline glass with a hydrophobic and oleophobic composite coating on the surface of microcrystalline glass with high crystallinity, and particularly relates to coated microcrystalline glass with a fluorine polymer hydrophobic and oleophobic layer, and a preparation method and application thereof. Background Glass generally has a relatively high surface activity, and therefore has poor hydrophobicity and hydrophobicity, that is, is easy to adhere to dirt, and is difficult to clean after the dirt on the surface. In many application scenes, such as kitchen ranges, kitchen ventilator glass products, mobile phones, tablet computers, touch screen man-machine interaction windows and the like, people adopt a layer of hydrophobic film to plate the surface of glass to reduce the surface activity of the glass, so that the hydrophobic and oleophobic capacity of the glass is improved, the hydrophobicity of the glass is improved, after the hydrophobic capacity is increased, the finger can obviously feel the improvement of the sliding property when touching the surface of the glass, and the sliding friction coefficient is reduced due to the improvement of the hydrophobicity, so that the touch interface is a function of improving the user experience. In the prior art, in order to improve the hydrophobic and oleophobic properties of the glass surface, a method of directly coating a film on the glass surface is generally adopted. A typical coating material is PFPE (one of perfluoropolyether-Per Fluoro Poly Ether, fluoropolyether silicon oxides) having the structure shown in formula (1) below, such as an alkoxy silicide: (1); wherein R can be carbon, hydrogen or silicon element, Y can be ether bond, sulfur-containing alkyl, sulfur-containing alkoxy, nitrogen-containing alkyl, nitrogen-containing alkoxy, epoxy alkyl, acyloxy alkyl, thio, etc. The process of connecting PFPE and glass is a chemical reaction process, PFPE is hydrolyzed (PFPE-Si-OR+H 2 O- > PFPE-Si-OH+ROH), and dehydration condensation reaction (as shown in figure 1, PFPE-Si-OH+H-O-Si- > H 2 O+PFPE-Si-O-Si-), and finally the PFPE film and the Si-O structure on the glass interface form valence bond connection, rather than the physical phenomenon of connecting by Van der Waals force between molecules as in most vacuum coating films. The prior art coating method is generally as follows. In view of the large number of Si-O structures in glass, PFPE has conditions to react directly with glass to form a film, but the mass ratio of SiO 2 in glass is usually not more than 70%, so that in order to improve the film coating effect and durability, the following two film coating methods are generally adopted: a) The dry method is called as a vacuum plating method, a SiO 2 plating layer is plated on the surface of the glass in vacuum, the Si-O proportion is increased, and then a PFPE layer is plated in a vacuum environment; b) The wet method is also called a spray coating method, wherein plasma is firstly used for bombarding the glass surface in the atmosphere, on one hand, the glass surface is cleaned, on the other hand, the glass surface is roughened, the glass surface area is increased under the microcosmic condition, the Si-O ratio is indirectly improved, and then a layer of PFPE solution is sprayed. The prior patent CN208747932U discloses a structure of a transparent glass ceramic surface antifouling coating, which is characterized in that the outer surface layer of a glass ceramic body (1) is attached with a colorless transparent antifouling layer (11) with the thickness of 4-30nm, and the antifouling layer (11) is a fluorosilicone hydrolytic compound. Wherein, the patent describes that the microcrystalline glass device is characterized in that a silicon dioxide layer with the thickness of 3-20nm is arranged below the anti-fouling layer (11). But the glass-ceramic of this patent is characterized by that "the mass ratio of crystal phase to glass phase in the glass-ceramic body is 0.25-1.2", belonging to the glass-ceramic with lower crystallinity, the glass phase in the glass-ceramic body is uniformly wrapped around the crystal phase, and the glass phase has alkali metal ions of sodium, lithium and potassium, etc., and the value of dividing the mass of alkali metal oxide in the glass phase by the mass of alumina and silica is 6% -30%, the crystallinity in the glass-ceramic is 20-54.54%, and the Si-O structure in the glass phase in the glas