Nova Patents
EP4036070B1

Coated microcrystalline glass with improved water-repellent and oil-repellent property, preparation method and application thereof

Abstract

This record has no abstract on file.

EP4036070B1, drawing sheet 1
Sheet 1 of 6

Term

15.3 yearsleft in the term

Expires 25 January 2042.

  1. Priority and filed
  2. Granted
  3. Today
  4. Expires

15 claims: 10 independent, 5 dependent

  1. 1
    A microcrystalline glass containing a water-repellent and oil-repellent composite coating layer on the surface, characterized in that from the outermost surface of the microcrystalline glass, it includes:a water-repellent and oil-repellent layer, an intermediate layer and a bottom layer, wherein, the intermediate layer is the intermediate layer containing ionic crystals with a lattice energy of 700-3000kJ/mol;wherein, the intermediate layer is a crystal layer formed by at least one ionic crystal of LiF, NaF and/or KF as the original coating material;or formed by at least one of MgF 2 , CaF 2 , SrF 2 or BaF 2 as the original coating material;the thickness of the intermediate layer is 1-5nm;the thickness of the bottom layer is 3-15nm;and the bottom layer includes compounds containing Si-O bonds or a mixed silicon oxide layer;and the microcrystalline glass's crystallinity is greater than 60%.
  2. 5
    The microcrystalline glass according to any one of claims 1-4, characterized in that the intermediate layer is a polar or non-polar compound;preferably a polar compound.
  3. 6
    The microcrystalline glass according to any one of claims 1-5, characterized in that the thickness of the intermediate layer is 1-2nm;and/or the thickness of the bottom layer is 5-10nm, and more preferably 5-8nm;and/or the thickness of the water-repellent oil-repellent layer is not less than 10nm, preferably not less than 15nm, which can be 10nm-25nm;preferably, the water-repellent oil-repellent layer is a fluorine-based polymer layer, more preferably, a fluorine-containing polyether silicon oxide layer with a molecular weight not less than 2000.
  4. 7
    The microcrystalline glass according to any one of claims 1-6, characterized in that when the bottom layer is a multilayer bottom layer, the compound containing Si-O bond or the mixed silicon oxide layer is as the outermost bottom layer, the mixed silicon oxide is a mixture of silicon oxide SiO x and oxides of at least one other element other than silicon and/or magnesium fluoride, wherein x is less than or equal to 2;preferably, the other element is element(s) of aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc or boron;more preferably the mixed silicon oxide is a mixture of silicon oxide SiO x and aluminum oxide;more preferably, the compound containing Si-O bond is SiO x , wherein x is less than or equal to 2;or any one of SiOC, SiON, SiOCN and/or Si 3 N 4 , or a compound with hydrogen bond bonded to any of SiO x , SiOC, SiON and/or SiOCN in any proportion, wherein x is less than or equal to 2.
  5. 8
    The microcrystalline glass according to any one of claims 1-7, characterized in that the microcrystalline glass contains oxides in the following mol%:SiO 2 : 40-75%, preferably 45-72%;Al 2 O 3 : 2-20%, preferably 4-15%;B 2 O 3 : 0-20%, preferably 0.4-1.6%;P 2 O 5 : 0-10%, preferably 0.8-1.5%;ZrO 2 +TiO 2 : 0-15%, preferably 0.9-4%;MgO:0-5%, preferably0.1-2%;ZnO: 0-4%, preferably 0.9-3.0%;rare earth oxide: 0-5%, preferably 0.01-1%;Na 2 O: 0-5.5%;K 2 O: 0-4%;Li 2 O: 2-34%, preferably 10-34%;and Na 2 O+K 2 O+Li 2 O: 4-40%, preferably 15-40%;the microcrystalline glass is a glass with or without ion exchange;Preferably, the rare earth oxide is selected from more than one or two of CeO 2 , Y 2 O 3 , La 2 O 3 , Ta 2 O 3 , Tm 2 O 5 and Nd 2 O 5 .
  6. 9
    The microcrystalline glass according to any one of claims 1-8, characterized in that the microcrystalline glass can also contain coloring additives and/or a clarifying agent;preferably, the coloring additive is one or more selected from Nd 2 O 3 , Fe 2 O 3 , CoO, NiO, V 2 O 5 , MnO 2 , TiO 2 , CuO and Cr 2 O 3 ;and/or the clarifying agent is one or more selected from As 2 O 3 , Sb 2 O 3 , SnO 2 , chloride, fluoride, compounds containing SO 3 - , and the compounds containing NO 3 - and preferably one or more selected from SnO 2 , compounds containing SO 3 - , chloride, and the compounds containing NO 3 - ;more preferably, the molar content of coloring additives shall not exceed 5% relative to the overall composition of the glass;further more preferably, in the molar content relative to the overall composition of the glass, the coloring additive contains more than 0.5mol% CoO and/or Cr 2 O 3 , and further more preferably contains more than 1mol% anyone selected from Fe 2 O 3 , NiO or MnO 2 ;and/or more preferably the content of the clarifying agent is 0-2mol%.
  7. 10
    The microcrystalline glass according to any one of claims 1-9, characterized in that the primary crystal phase of the microstalline glass is one or more selected from beta quartz solid solution, beta spodumene solid solution, beta lithium nepheline, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, silica, zirconia, magnetite;preferably the average crystal grain size is less than 100nm, preferably less than or equal to 50nm, especially preferably less than or equal to 30nm.
  8. 11
    The preparation method of the microcrystalline glass according to any one of claims 1-10, including the following steps:1) coating microcrystalline glass with a layer containing Si-O oxide or mixed silicon oxide, to form a bottom layer on the surface of the microcrystalline glass;2) an intermediate layer is coated on the surface of the bottom layer obtained in Step 1);3) a water-repellent and oil-repellent layer is coated on the surface of the intermediate layer obtained in Step 2).
  9. 14
    The preparation method according to any one of claims 11-13, characterized in that the microcrystalline glass is formed by a firing method containing the following steps before coating the bottom layer, the intermediate layer and the water-repellent and oil-repellent layer:(I) the glass raw materials are melted at 1600 ± 50°C, and then annealed at 400-650°C to get a homogenized mother glass plate;(II) the mother glass plate is formed into a molding mother glass plate by an overflow flow, float or calendering process;and (III) the molding mother glass plate is micro crystallized by secondary heat treatment to give a microcrystalline glass preform, then it is ion exchanged or directly used as the raw material of microcrystalline glass without ion exchange, for coating the needed bottom layer, the intermediate layer and the water-repellent and oil-repellent layer on its surface coating layer, wherein the first heat treatment temperature is 500-1000°C, the secondary heat treatment temperature is 550-1100°C.
  10. 15
    Use of the microcrystalline glass according to any one of claims 1-10 or the microcrystalline glass obtained by the preparation methods according to any one of claims 11-14 in mobile phone display screen, laptop display screen, notebook display screen, handheld game consoles, portable digital device, on-board display screen, windshield or camera screen.
Independent claims10