Transport vehicle glazing with water repellent and anti-dust coating associated with a detection device

Abstract

A vehicle glazing includes on its surface to be exposed to the exterior atmosphere, at least in a zone not wiped by the windscreen wipers, a mineral oxide layer of 0.1 to 20 m thickness, 30 to 90% of the volume of which consists of 20 to 300 nm open pores that are distributed uniformly throughout the thickness of the layer, and almost all of which are connected to one another, the internal and external surface of the layer being functionalized with a compound containing a perfluoroalkyl or alkyl functional group, then saturated with a hydrophobic oil that impregnates the functionalized porous layer and forms a film on the surface thereof, the at least one zone being located facing a detecting device such as an anti-collision/obstacle-detecting/security video camera, or similar, placed in the interior of the vehicle, in particular on the face of the glazing.

Claims

1. A transport vehicle glazing comprising a first side to face an interior of a transport vehicle and a second side to face an exterior atmosphere, the second side being opposite the first side, at least one zone of the second side not wiped by windscreen wipers and facing the exterior atmosphere, and said at least one zone being located to face a detecting device placed in the interior of the transport vehicle, wherein the transport vehicle glazing comprises a substrate and a mineral oxide layer provided on the substrate, the mineral oxide layer being of 0.1 to 20 m thickness, wherein 30% to 90% of the volume of the mineral oxide layer consists of 20 to 300 nm open pores that are distributed uniformly throughout the thickness of the mineral oxide layer, and a majority of the open pores are connected to one another, an internal surface and an external surface of the mineral oxide layer being functionalized with a compound containing a perfluoroalkyl or alkyl functional group, saturated with a hydrophobic oil that impregnates the functionalized porous layer and forms a film on the surface thereof, and wherein the mineral oxide layer is made of silica and formed at least in the zone of the second side not wiped by windscreen wipers and facing the exterior atmosphere.

2. The glazing as claimed in claim 1, wherein 40% to 90% of the volume of the mineral oxide layer consists of open pores.

3. The glazing as claimed in claim 2, wherein from 50% to 90% of the volume of the mineral oxide layer consists of open pores.

4. The glazing as claimed in claim 1, wherein 30% to 80% of the volume of the layer consists of open pores.

5. The glazing as claimed in claim 1, wherein the open pores are from 30 nm to 300 nm in size.

6. The glazing as claimed in claim 5, wherein the open pores are from 50 nm to 300 nm in size.

7. The glazing as claimed in claim 1, wherein the open pores are from 20 nm to 200 nm in size.

8. The glazing as claimed in claim 1, wherein the hydrophobic oil comprises at least one compound selected from the group consisting perfluorinated hydrocarbons or organic silicones; perfluoropolyethers, perfluoroalkylethers and perfluorocycloethers; tertiary perfluoroalkylamines; perfluoroalkylsulfides and perfluoroalkylsulfoxides; perfluoroalkylphosphines and oxidation products thereof; perfluorinated carboxylic acids; fluorinated phosphonic and sulfonic acids; fluorinated silanes; and any combinations thereof.

9. The glazing as claimed in claim 1, wherein the detecting device is an anti-collision/obstacle-detecting/security video camera.

10. The glazing as claimed in claim 1, wherein the detecting device is placed on the first side of the glazing.

11. A process for manufacturing a transport vehicle glazing that comprises a first side to face an interior of a transport vehicle and a second side to face an exterior atmosphere, the second side being opposite the first side, the process comprising in succession: depositing on a substrate a liquid pore-forming agent composition and one or more mineral oxide precursors; calcinating the obtained assembly of the substrate coated with the liquid pore-forming agent composition and the one or more mineral oxide precursors to remove the pore-forming agent and form a condensed porous mineral oxide layer of 0.1 to 20 m thickness on the substrate, wherein 30 to 90% of the volume of the mineral oxide layer consists of 20 to 300 nm open pores that are distributed uniformly throughout the thickness of the mineral oxide layer, and a majority of the open pores are connected to one another; grafting onto an external surface and an internal surface of the porous mineral oxide layer said compound containing a perfluoroalkyl or alkyl functional group to functionalize the internal and the external surfaces of the porous mineral oxide layer, then pouring an excess of hydrophobic oil onto the functionalized mineral oxide layer of the substrate, the hydrophobic oil impregnating the functionalized mineral oxide layer and forming a film on the surface thereof, the substrate being held inclined in order to remove excess oil from the substrate, wherein the mineral oxide layer is made of silica and formed at least in a zone of the second side not wiped by windscreen wipers and facing the exterior atmosphere, and said at least one zone being located to face a detecting device placed in the interior of the transport vehicle.

12. The process as claimed in claim 11, wherein the mineral oxide is formed from silica precursors comprising glycidoxypropyltrimethoxysilane and tetraethoxysilane.

13. The process as claimed in claim 11, wherein the pore-forming agent is selected from the group consisting of a latex of acrylic particles and a meth(acrylic) polymer emulsion.

14. The process as claimed in claim 13, wherein the pore-forming agent is formed from a latex of particles of polymethyl methacrylate.

15. The process as claimed in claim 11, wherein the liquid pore-forming agent composition and the one or more mineral oxide precursors are deposited on the substrate by roller, spraying, dip-coating, screen printing with adjustment of the rheology or inkjet printing.

16. The process as claimed in claim 11, wherein the compound containing a perfluoroalyl functional group has the formula: ##STR00003## in which m=0 to 15; n=1 to 5; p=0, 1 or 2; R is an alkyl group or a hydrogen atom; and X represents a hydrolysable group; or consists of a perfluoropolyethersilane represented by the formula (II) ##STR00004## or by the formula ##STR00005## in which: m=2 to 30; n=1 to 3; p=0, 1 or 2; R is an alkyl group or a hydrogen atom; and X is a hydrolysable group; or consists of a perfluoropolyether bearing an alkoxysilane group at two ends having the following formula
R.sub.1OSiR.sub.2R.sub.3R.sub.4[(CF.sub.2).sub.nO]R.sub.5R.sub.6R.sub.7SiOR.sub.8 wherein R.sub.1O and OR.sub.8 are alkoxy groups, R.sub.2-7 are alkyl groups optionally comprising one or more heteroatoms, n and m being integers of 1 or more.

17. The process as claimed in claim 16, wherein, in formula I, m=5 to 11.

18. The process as claimed in claim 11, wherein, before the compound containing a perfluoroalkyl or alkyl functional group is grafted, the internal and external surfaces of the porous mineral oxide layer are hydrophilic, and wherein a graft precursor containing a perfluoroalkyl or alkyl functional group is hydrolyzed to condense with the surface of the porous mineral oxide layer to obtain the graft.

Description

EXAMPLE

(1) A glycidoxypropyltrimethoxysilane (GLYMO) solution is prepared by mixing 10 g of GLYMO and 2.25 g of pH=2 HCl solution under agitation at room temperature for about 2 h.

(2) A tetraethoxysilane (TEOS) solution is prepared by mixing 4 g of TEOS and 6 g of pH=2 HCl solution under agitation at room temperature for about 2 h.

(3) A GLYMOS-TEOS sol is prepared by mixing 1 part of GLYMO sol to 2 parts of TEOS sol (by weight).

(4) The solution to be deposited is prepared by mixing 0.98 g of the GLYMO-TEOS sol prepared above, 0.59 g of the methacrylic polymer emulsion sold under the registered trademark NeoCryl XK-52 by DSM, 3.4 g of pH=2 HCl solution, and 0.5% by weight of the fluorinated surfactant sold under the registered trademark Novec FC-4430 by 3M.

(5) This solution is deposited by roller on a sample of soda-lime-silica float glass of 10 cm10 cm area and 4 mm thickness.

(6) The sample is calcinated at 450 C. with the aim of degrading the pore-forming agent (NeoCryl XK-52). A crack- and splinter-free condensed porous silica layer of 1.7 m thickness and 60% porosity is obtained with pores of 60 nm size, the pores almost all being connected to one another throughout the thickness of the coating.

(7) A mixture of 213 L of 1H,1H,2H,2H-perfluorodecyltriethoxysilane (designated SiF7 below) respecting the formula F.sub.3C(CF.sub.2).sub.7(CH.sub.2).sub.2Si(OC.sub.2H.sub.5).sub.3, of 9 g of isopropanol (IPA) and of 1 g of 0.1N HCl is then prepared. This mixture has a pH=1. SiF7 is hydrolyzed therein, i.e. each of the three ethoxy groups is replaced by a hydroxy group OH therein.

(8) The surface of the condensed porous silica layer prepared above is made hydrophilic with a 60-minute UV-ozone treatment at 50 C., then the hydrolyzed SiF7 mixture prepared above is wiped (i.e. deposited by means of an imbibed cloth) onto the surface of the hydrophilic porous layer in order to condense the SiOH groups of the SiF7 with those of the porous layer by forming SiOSi bonds. Instead of wiping, the hydrolyzed SiF7 mixture may also be deposited by spraying.

(9) The sample is then baked at 150 C. for 30 to 60 minutes.

(10) Onto the porous layer thus functionalized by SiF7, an excess of perfluoropolyether oil respecting the following formula is poured:
F(CFCF.sub.3CF.sub.2O).sub.nCF.sub.2CF.sub.3
with n comprised between 10 and 60,

(11) viscosity of 12.6 cP,

(12) this oil being that sold by Du Pont under the registered trademark Krytox GL 100 . The sample is held inclined in order to remove excess oil from the substrate. The amount of oil retained thereby is at least equal to 0.5 ml/cm.sup.2.

(13) A droplet of water on the surface of the coating consisting of the porous layer+SiF7+Krytox does not spread and runs off even when the sample is held flat. The coating is hydrophobic and the water-immiscible fluorinated liquid prevents any adhesion of the droplet via capillary action. A small inclination (5) is enough to make the droplet run off the sample, leaving no trace.

(14) The repellent coating is durable in two respects: The fluorinated oil remains durably impregnated in the porous layer even though it is fluid and is doubtlessly removed in small amounts by water droplets running over the surface. A 200 mm volume of water applied in drops to a given point of the surface of the sample does not diminish the repellency properties. Cleaning of the coating or a very-long-term use implies gradual removal of the oil. Nevertheless, the latter may be easily reapplied to the surface of the sample (coated with the porous layer functionalized with the remaining oil) in order to allow it to recover a performance equivalent to when first used.

(15) Moreover, this repellency property gives the coating dust-resistance and anti-frost functionalities.

(16) This repellent coating with its macroporous layer is very advantageous for glazings in which transparency is required and in which mark-resistance, dust-resistance and/or anti-frost functionalities are desired. It is particularly advantageous, in the context of the invention, to coat that zone of the windshield of automobiles behind which the obstacle-detecting video camera (more and more commonly used by automobile manufacturers) or equivalent is located.