 optical article comprising a temporary anti-fog coating with improved durability
专利摘要:
optical article comprising a temporary anti-fog coating with improved durability. the present invention relates to an optical article comprising a substrate provided with a coating comprising silanol groups on the surface thereof, directly in contact with this coating, a precursor coating of the anti-fog coating, said precursor coating having a contact angle static with water of more than 10 and less than 50, a thickness less than or equal to 5nm, and being obtained by grafting at least one organosilane compound having a polyoxyalkylene group comprising less than 80 carbon atoms and at least one atom of silicone giving at least one hydrolyzable group. the precursor anti-fog coating is converted into a current anti-fog coating by applying a film of a liquid solution comprising at least one surfactant to the surface. the anti-fog coating is immediately operational and provides long-lasting effects. 公开号:BR112012016406B1 申请号:R112012016406 申请日:2010-12-22 公开日:2020-04-14 发明作者:Henky Francis；Cadet Mamonjy；Feuillade Mathieu 申请人:Essilor Int Comagnie Generale Doptique；Satisloh Ag； IPC主号:
专利说明:
“OPTICAL ARTICLE UNDERSTANDING A TEMPORARY ANTI-SMOOTHING COAT WITH IMPROVED DURABILITY” [0001] The present invention relates to an optical article provided with a coating comprising silanol groups on its surface, typically an anti-reflective coating, which have been modified to allow an efficient and long-term application of a fog-free solution, as well as a method for making such an optical article. [0002] Various numerous supports, such as plastic materials and glass, suffer from a disadvantage when they become covered with fog, when their surface temperature is below the dew point of the ambient air. This is specifically the case with glass that is used to coat windows for transport vehicles or buildings, display glass, lenses, mirrors and the like. The fog that develops on these surfaces leads to a decrease in transparency, due to the diffusion of light through drops of water, which can cause substantial discomfort. [0003] To prevent any mist formation in humid environments, that is, the condensation of very small water droplets on a support, it has been suggested to apply hydrophilic coatings on the external surface of such support, with a low static contact angle with water, preferably less than 50 o , more preferably less than 25 o . Such permanent anti-fog coatings act as sponges for the mist and allow water droplets to adhere to the surface of the support by forming a very thin film that gives an impression of transparency. These coatings are generally made from highly hydrophilic species such as sulfonates or polyurethanes. [0004] Commercially available products comprise several hydrophilic layers of micrometric thickness. [0005] As a rule, when the thickness of the coatings is high (several microns), these coatings, as a consequence of water absorption, swell, soften and become mechanically less resistant. [0006] As used herein, a permanent anti-fog coating is Petition 870190016216, of 02/18/2019, p. 11/116 2/49 intended to mean a coating whose hydrophilic properties result from hydrophilic compounds permanently bonded to another coating or support. EP 1324078 describes a coated lens with high and low refractive indexes alternating with each other, among which the outer layer is a low refractive index layer (1.42-1.48) of about 5 to 100 nm thickness forming an anti-fog coating consisting of a hybrid layer with a static contact angle with water of less than 10 o , obtained by vacuum deposition of both, simultaneously, an organic compound and silica or silica and aluminum, which is say through the co-evaporation of these various components. The anti-fog coating preferably comprises from 0.02 to 70% by weight of the organic compound relative to the total weight of the coating, and typically from 6 to 15% by weight, according to the examples. [0007] The said organic compound comprises a hydrophilic group and a relative group, for example, a trialcoxysilyl group having 3 to 15 carbon atoms, and preferably has a molecular weight ranging from 150 to 1500 g / mol. Some preferred compounds have a polyether structure, especially a polyoxyethylene and a reactive group at each end of the molecule. Preferred compounds include polyethylene glycol glycidyl ether, polyethylene glycol monoacrylate and N- (3-trimethoxysilylpropyl) gluconamide. [0008] The anti-fog coating thus becomes like a layer based on silica (or a layer based on silica + alumina) incorporating a hydrophilic organic compound. However, its anti-fog character changes over time, and the deterioration of anti-fog properties can be gradually observed. When it becomes too low, they can be restored through a “wash treatment” of the anti-fog film, particularly a plasma-mediated treatment. [0009] In practice, the co-evaporation method of application EP 1324078 is very complicated to implement. It may be preferable to have a method of making an anti-fog coating without performing any co-evaporation process. Petition 870190016216, of 02/18/2019, p. 11/12 3/49 [0010] US patents US 6,251,523 and US 6,379,776 describe an anti-reflective, anti-fog glass for cars or lenses, comprising a glass substrate provided with an antireflective coating based on 110-250 nm silica. thickness with a Ra roughness surface of about 5-10 nm, then provided with a permanent 8 nm thick anti-fog coating obtained through a liquid or vapor deposition of the compound CH3O (CH2CH2O) 6-9- ( CH2) 3Si (OCH3) 3 or a hydrolyzate thereof. In the initial stage, the anti-fog coating has a statistical contact angle with water of 3 o . [0011] Another solution to combine anti-reflective and anti-fog properties is the use of a thin porous layer of low refractive index, partially made of surfactants, which allow the layer to acquire anti-fog properties. This layer is usually deposited on a hydrophilic surface. [0012] So, US patent 5,997,621 describes a porous anti-fog and anti-reflective coating based on metal oxides (silica spheres) and anionic surfactants relatively soluble in water, generally having a hydrophilic ionic head of the carboxylic acid type, sulfonate, or phosphate and a fluorinated chain. In order to be immobilized on a substrate, surfactants are preferably capable of covalently bonding to metal oxides. WO 97/43668 describes a similar construction. [0013] EP application 0871046 describes an anti-reflective and anti-fog system comprising a porous layer based on inorganic oxide deposited in a water-absorbing layer of a few micrometers thick, obtained by poly-condensation of a hydrolyzed inorganic alkoxide in the presence of a polyacrylic acid compound. The porous layer, which acts as an anti-reflective barrier allows water to access the absorbent layer. [0014] Anti-fog properties can also be obtained by applying temporary solutions commercially available as sprays or small wipes, on display glasses comprising an outer layer of an anti-dirt coating (hydrophobic and oleophobic), always considered as Petition 870190016216, of 02/18/2019, p. 11/13 4/49 essential when ophthalmic glass is provided with an anti-reflective coating. They make it possible to obtain the anti-fog property in a short period of time. The ease of the dirt removal aspect that is given to the anti-dust coating is preserved, but after a couple of drying operations, the anti-fog property is significantly altered. In fact, temporary solutions comprise materials that are hydrophilic in nature with poor interactions with the hydrophobic anti-dirt coating surface, so that after a few smear operations, these hydrophilic materials are removed. [0015] A more interesting solution is to make an anti-fog coating by applying a temporary hydrophilic solution to the surface of a precursor anti-fog coating, which represents an alternative to permanent anti-fog coatings. [0016] EP application 1275624 describes a lens coated with a hard inorganic hydrophilic layer based on metal oxides and silicon oxide. Its hydrophilic nature and the presence of concave portions of nano size on its surface allow to impregnate a surfactant and retain the same adsorbed for a long period of time, thus maintaining an anti-fog effect for several days. However, an anti-fog effect can also be observed in the absence of any surfactant. [0017] JP 2004-317539 and JP 2005-281143 applications describe a lens coated with a multi-layer anti-reflective coating and / or with an abrasion resistant coating and with a precursor coating to the anti-fog coating, having a static contact angle with water of about 50 o to 90 o . The anti-fog coating such as, which is a temporary coating, is obtained after application of a surfactant on the surface of the precursor coating. [0018] The precursor coating of the anti-fog coating is obtained from a composition comprising an organic compound comprising a hydrophilic group of a polyoxyethylene nature, a reactive group capable of reacting with the outer layer of the anti-reflective coating, especially a layer based on silica , such as Si (OR) n alkoxysilane groups, SiOH silanol or Petition 870190016216, of 02/18/2019, p. 11/146 5/49 isocyanate, and optionally a fluorinated hydrophobic group, and the composition is chosen so that the angle of static contact with water of the anti-fog coating precursor ranges from 50 o to 90 o . The organic compounds used in the anti-fog coating precursor preferably have a molecular weight having from 700 to 5000 or from 430 to 3700 g / mol. To be mentioned as examples of such compounds are the compounds CH3O (CH2CH2O) 22CONH (CH2) 3Si (OCH3) 3 or C8F17O (CH2CH2O) 2CONH (CH2) 3Si (OCH3) 3. The precursor coating is described as being 0.5 to 20 nm thick. The relatively high contact angle of the precursor coating is expected because it allows, according to these requests, to easily remove dirt resulting from the drying of water droplets. [0019] However scientists are still looking for temporary anti-fog coating compositions from which layers can be formed using easy-to-implement methods, whose anti-fog properties can be more efficient, which can last longer over time and / or under mechanical stresses, while maintaining acceptable cleanability. [0020] Anti-fog coatings also having good mechanical properties (abrasion and scraping resistance) are still in demand. [0021] The present invention aims to prepare such temporary anti-fog coatings, which significantly improve the anti-fog durability property, while maintaining good mechanical properties. [0022] It is an additional object of the present invention to provide a fog-resistant coating that can be immediately operational, that is, a coating that, when a transparent glass substrate coated with such a coating is placed under mist-generating conditions on said substrate being devoid of the said coating, it allows to immediately reach (that is, in less than a second) a vision> 6/10 (visual acuity), and preferably of 10/10, without fog formation for an observer looking through a glass coated with according to the visual acuity scale Snellen E (ARMAIGNAC scale (Tridents) (Snellen E) reading in 5M, ref. T6 available from FAX INTERNATIONAL), located at a distance of 5 meters. Petition 870190016216, of 02/18/2019, p. 11/15 It is an additional object of the present invention to provide an optical article having both anti-reflective and anti-fog properties. [0024] These objectives can be pursued, according to the invention, thanks to a modification of silanol groups on the surface of an optical article, by grafting a particular organosilane compound. [0025] Then, the present invention relates to an optical article, preferably a lens for glasses, comprising a substrate provided with a coating comprising silanol groups on the surface of the same and, directly in contact with this coating, a precursor coating of the coating anti-fog, thus characterizing the precursor coating to the anti-fog coating: - is obtained by grafting at least one organosilane compound having: - a polyoxyalkylene group, and - at least one silicon atom having at least one hydrolyzable group, - has a thickness less than or equal to 5 nm, - has a static contact angle with water of more than 10 o and less than 50 o . [0026] The present invention further relates to an optical article, preferably a lens for glasses, as above, the precursor coating of anti-fog coating which is furthermore coated with a film of a liquid solution comprising at least a surfactant. In other words, such an optical article is provided with a temporary anti-fog coating according to the invention. [0027] The invention will be described in more detail with reference to the attached drawing showing in Figure 1 the evolution, as a function of time, of the anti-fog properties of optical articles according to the invention and comparative optical articles, initially exposed to hot steam. Petition 870190016216, of 02/18/2019, p. 11/16 7/49 [0028] In the present application, a coating that is "positive" on the substrate / coating or that has been deposited "on" a substrate / coating is defined as a coating that (i) is positioned above the substrate / coating, (ii) is not necessarily in contact with the substrate / coating, that is, one or more intermediate coatings can be arranged between the substrate / coating and the coating in question (however, it is preferably in contact with said substrate / coating), and (iii) does not necessarily completely cover the substrate / coating. When “a layer 1 is arranged over a layer 2”, it is intended to mean that layer 2 is more distant from the substrate than layer 1. [0029] As used herein, an "anti-fog coating" is intended to mean a coating that, when a transparent glass substrate coated with such a coating is placed under conditions generating mist on said substrate being stripped of said coating, allows to immediately achieve a visual acuity of> 6/10 by an observer looking through coated glass on a visual scale located at a distance of 5 meters. Various tests to assess the anti-fog properties of a coating are described in the experimental section. Under fog-generating conditions, anti-fog coatings may not have fog on their surface (ideally no visual distortion, or visual distortion, but visual acuity of> 6/10 over the measurement conditions mentioned above), or may present some fog. on its surface, but still allow, despite the visual disturbance resulting from fog, a visual acuity of> 6/10 on the measurement conditions mentioned above. A non-fog coating does not allow a visual acuity of> 6/10 while it is exposed to mist-generating conditions and generally presents a condensed mist over the measurement conditions mentioned above. [0030] As used herein, an "anti-fog glass" is intended to mean a glass provided with an "anti-fog coating" as defined above. Petition 870190016216, of 02/18/2019, p. 11/176 8/49 [0031] Therefore, the precursor anti-fog coating according to the invention, which is a hydrophilic coating, is not considered to be an anti-fog coating according to the present invention, even if it has some anti-fog properties. foggy, which can be observed, for example, by means of a breath test described in the experimental section. In fact, this anti-fog coating precursor does not allow to obtain a visual acuity> 6/10 under the measurement conditions mentioned above, as shown in Figure 1, which will be discussed later. [0032] As used herein, a temporary anti-fog coating is intended to mean an anti-fog coating obtained after applying a liquid solution comprising at least one surfactant on the surface of a precursor coating of said anti-fog coating. The durability of a temporary anti-fog coating is generally limited by drying operations carried out on the surface, the surfactant molecules being not permanently attached to the surface of the coating, but only adsorbed for a more or less durable period of time. [0033] The optical article prepared according to the invention comprises a substrate, preferably transparent, having front and back main surfaces, at least one of said main surfaces being provided with a coating comprising silanol groups on the surface thereof, preferably both surfaces main. As used herein, the back surface (usually concave) of the substrate is intended to mean the face which, when using the article, is the closest to the user's eye. On the contrary, the front face (usually convex) of the substrate, is the face that, when using the article, is the furthest from the user's eye. [0034] Although the article according to the invention can be any optical article that may encounter a misting problem, such as a screen, a glass for the automotive or construction industry, or a mirror, it is preferably a lens optics, more preferably an ophthalmic lens, for glasses, or a blank for ophthalmic or optical lenses. Petition 870190016216, of 02/18/2019, p. 11/186 9/49 [0035] These articles exclude articles such as intraocular lenses that are in contact with living tissue or contact lenses, which do not intrinsically face the problem of mist formation, as opposed to glasses for glasses. [0036] According to the invention, the coating comprising silanol group on its surface can be formed on at least one of the main surfaces of a substrate only, that is to say an uncoated substrate, or at least one of the main surfaces of a substrate that has already been coated with one or more functional coatings. [0037] The substrate for the optical article according to the invention can be a mineral or an organic glass, for example, of a thermoplastic or thermoset plastic material. [0038] Especially preferred classes of substrates include poly (thiourethanes), polyepisulfides and resins resulting from the polymerization or (co) polymerization of alkylene glycol bis allyl carbonates. These are solid, for example, under the trademark CR-39® by the company PPG Industries (ORMA® lenses, from ESSILOR). [0039] In some applications, it is preferred that the main surface of the substrate is coated with one or more functional coatings prior to depositing the coating comprising silanol groups on its surface. Such functional coatings traditionally used in optics can be without limitation, an impact resistant primer layer, an abrasion resistant coating and / or a scratch resistant coating, a polarized coating, a photochromic coating or a painted coating, particularly a resistant initiator layer impact coated with an abrasion resistant layer and / or scratch resistant coating. [0040] The coating comprising silanol groups on the surface thereof is preferably deposited on the abrasion resistant and / or scratch resistant coating. The abrasion resistant and / or scratch resistant coating can be any layer traditionally used as an abrasion resistant coating and / or scratch resistant coating in the fields of ophthalmic lenses. Petition 870190016216, of 02/18/2019, p. 11/196 10/49 [0041] Abrasion resistant and / or scratch resistant coatings are preferably hard coatings based on poly (meth) acrylates or silanes generally comprising one or more mineral fillers which are intended to improve the hardness and / or refractory index of the coating once healed. As used herein, a (meth) acrylate is an acrylate or a methacrylate. [0042] The abrasion resistant coating and / or scratch resistant hard coatings are preferably made from compositions comprising at least one alkoxysilane and / or hydrolyzate thereof, obtained, for example, by hydrolysis with hydrochloric acid solution, and optionally condensation and / or catalyzed curing and / or surfactants. Recommended coatings of the present invention include coatings based on hydrolyzed epoxysilane such as those described in EP 0614957, US 4,211,823 and US 5,015,523. [0044] The thickness of the abrasion resistant coating and / or scratch resistant coating generally varies from 1 to 10 pm, preferably from 3 to 5 pm. [0045] Before deposition of the abrasion resistant coating and / or scratch resistant coating, it is possible to apply an initiator coating to the substrate to improve the impact resistance and / or adhesion of the subsequent layers in the final product. [0046] This coating can be any impact resistant initiator layer traditionally used for articles in a transparent polymer material, such as ophthalmic lenses. Preferred starter compositions include compositions based on thermoplastic polyurethanes, such as those described in JP 63-141001 and JP 63-87223, poly (meth) acrylic starter compositions, such as those described in U.S. Patent 5,015,523, compositions based on thermosetted polyurethanes, such as those described in EP 0404111 and compositions based on poly (meth) acrylic latex or polyurethane-type latex, such as those described in U.S. patents 5,316,791 and EP 0680492. Petition 870190016216, of 02/18/2019, p. 11/20 11/49 [0048] Preferred starter compositions are compositions based on polyurethanes and compositions based on latex, particularly polyurethane latex and poly (meth) acrylic latex, and combinations thereof. Initiating layers generally have a thickness, after curing, ranging from 0.2 to 2.5 pm, preferably ranging from 0.5 to 1.5 pm. [0049] The coating comprising silanol groups on the surface thereof will be described below. As used herein, a coating comprising silanol groups on the surface thereof is intended to mean a coating that naturally comprises silanol groups on the surface thereof or a coating whose silanol groups have been created after being subjected and a surface activation treatment. This coating is thus a coating based on siloxanes or silica, for example, without limitation, a layer based on silica, a sol-gel coating, based on organosilane species such as alkoxysilanes, or a coating based on silica colloids. It can be especially an abrasion resistant coating and / or a scratch resistant coating, or, according to the present embodiment, a monolayer anti-reflective coating or a multi-layer anti-reflective coating, the outer layer of which has silanol groups on its surface. As used herein, the outer layer of a coating is intended to mean the layer that is furthest from the substrate. [0050] The activating surface treatment generating the silanol groups or at least increasing their proportion on the surface of a coating is usually done under vacuum. It can be a bombardment with energetic and / or reactive species, for example, with an ion beam (“Ion Pre-Cleaning” or “IPC”) or with an electron beam, a treatment with radiation discharge, a treatment with ionic nuclear reaction, an ultraviolet treatment or a vacuum-mediated plasma treatment, usually using an oxygen or an argon plasma. It can also be an acidic or basic treatment and / or a solvent-based treatment (water, hydrogen peroxide or any organic solvent). Many of these treatments can be combined. Petition 870190016216, of 02/18/2019, p. 11/21 12/49 [0051] As used herein, energetic species (and / or reactive species) are intended to mean ionic species with an energy ranging from 1 to 300 eV, preferably from 1 to 150 eV, more preferably from 10 to 150 eV, and even more preferably from 40 to 150 eV. Energetic species can be chemical species such as ions, radicals or species such as photons or electrons. [0052] The activator treatment can also be an acidic or basic chemical surface treatment, preferably a wet treatment or a treatment using a solvent or a combination of solvents. [0053] The coating comprising silanol groups on the surface thereof preferably has a low refractive index based on silica (comprising silica), more preferably it consists of a layer based on silica (SiO2), generally obtained through vapor phase deposition. [0054] Said SiO2-based layer may comprise, in addition to silica, one or more other materials traditionally used to make thin layers, for example, one or more materials selected from dielectric materials described hereinafter in the present specification. This SiO2-based layer is preferably free of Al2O3. [0055] The inventors have observed that it is not essential to carry out a surface treatment when the layer is a silica-based layer, particularly when obtained through evaporation. The coating comprising silanol group on the surface thereof preferably comprises at least 70% by weight of SiO2, more preferably at least 80% by weight and even more preferably at least 90% by weight of SiO2. As already reported, in a more preferred embodiment, it comprises 100% by weight of silica. [0057] The coating comprising silanol groups on the surface thereof can also be a sol-gel coating based on silanes such as alkoxysilanes, for example, tetraethoxysilane or organosilanes such as γ-glycidoxypropyl trimethoxysilane. Such a coating is obtained through wet deposition, by using a liquid composition comprising a silane hydrolyzate and Petition 870190016216, of 02/18/2019, p. 11/22 13/49 optionally colloidal materials with a high refractive index (> 1.55, preferably> 1.60, more preferably> 1.70) or a low (<1.55). Such a layered coating comprises an organic / inorganic hybrid matrix based on silanes in which colloidal materials are dispersed to adjust the refractive index of each layer are described, for example, in the patent FR 2858420. [0058] In one embodiment of the invention, the coating comprising silanol groups on the surface thereof is a silica-based layer deposited in an abrasion resistant coating, preferably directly deposited in this abrasion resistant coating. [0059] Said silica-based layer (comprising silica) is preferably a silica-based layer, generally obtained through chemical vapor deposition. It preferably has a thickness less than or equal to 500 nm, more preferably ranging from 5 to 20 nm, and even more preferably from 10 to 20 nm. [0060] Preferably, the deposition of said silica-based layer is carried out by pressure regulation, which means by adding gas to the deposition chamber, the gas being in a non-ionic form, preferably by adding oxygen, at a pressure varying typically from 5.10 -5 to 5.10 -4 mbar. [0061] In another embodiment of the invention, which is the most preferred embodiment, the optical article according to the invention comprises an anti-reflective coating. When such a coating is present, it generally represents the coating comprising silanol group on the surface thereof within the meaning of the invention. The antireflective coating can be any antireflective coating traditionally used in optical fields, particularly ophthalmic optics, provided that it comprises silanol groups on its surface. [0062] An anti-reflective coating is defined as a coating, deposited on a surface of an optical article, which improves the anti-reflective properties of the final optical article. It makes it possible to reduce the light reflection at the article-air interface over a relatively large portion of the visible spectrum. Petition 870190016216, of 02/18/2019, p. 11/23 14/49 [0063] As is also well known, antireflective coatings traditionally comprise a monolayer or multilayer agglomerate composed of dielectric materials. These are preferably multilayer coatings, comprising layers with a high refractive index (HI) and layers with a low refractive index (LI). [0064] In the present application, a layer of anti-reflective coating is said to be a layer with a high refractive index when its refractive index is greater than 1.55, preferably greater than or equal to 1.6, more preferably greater than or equal to 1.8 and even more preferably greater than or equal to 2.0. A layer of an anti-reflective coating is said to be a low refractive index layer when its refractive index is less than or equal to 1.55, preferably less than or equal to 1.50, more preferably less than or equal to 1, 45. Unless otherwise specified, the refractive indices referred to in the present invention are expressed at 25 o C at a wavelength of 550 nm. [0065] HI layers are traditional layers with a high index of refraction, which are well known in the art. They generally comprise one or more metal oxides such as, without limitation, zirconia (ZrO2), titanium dioxide (TiO2), tantalum pentoxide (Ta2O5), neodymium oxide (Nd2O5), praseodymium oxide (Pr2O3), praseodymium titanate (PrTiO3), La2O3, Dy2O5, Nb2O5, Y2O3. [0066] LI layers are also well known and can comprise, without limitation, SiO2, MgF2, ZrF4, alumina (AUO3), AlF3, chiolite (Na3Al3F14]), cryolite (Na3 [AlF6]), and combinations thereof, preferably SiO2 or SiO2 together with alumina. Layers of SiOF (SiO2 together with fluorine) can also be used. [0067] When a LI layer comprising a mixture of SiO2 and Al2O3 is used, it preferably comprises from 1 to 10%, more preferably from 1 to 8% and even more preferably from 1 to 5% by weight of Al2O3 relative to SiO2 + Al2O3 total weight in this layer. [0068] Generally speaking, HI layers have a physical thickness ranging from 10 to 120 nm, and LI layers have a physical thickness ranging from 10 to 100 nm. Petition 870190016216, of 02/18/2019, p. 11/24 15/49 [0069] Preferably, the total thickness of the anti-reflective coating is less than 1 micrometer, more preferably less than or equal to 800 nm and even more preferably less than or equal to 500 nm. The total thickness of the anti-reflective coating is generally greater than 100 nm, preferably greater than 150 nm. [0070] Even more preferably, the anti-reflective coating comprises at least two layers with a low refractive index (LI) and at least two layers with a high refractive index (HI). Preferably, the total number of layers in the antireflective coating is less than or equal to 8, more preferably less than or equal to 6. [0071] Layers HI and LI do not need to alternate with each other in the antireflective coating, although they can also, according to one embodiment of the invention. Two HI layers (or more) can be deposited to each other, as well as two LI layers (or more) can be deposited to each other. [0072] The various layers in the antireflective coating were preferably deposited by vapor deposition, under vacuum, according to any of the following methods: i) by optionally assisted ion beam evaporation; ii) by ion beam emission; iii) by cathode emission; iv) by deposition of chemical vapor assisted by plasma. These various methods are described in the following references Thin Film Processes and Thin Film Processes II, Vossen & Kern, Ed., Academic Press, 1978 and 1991, respectively. A particularly recommended method is evaporation under vacuum. [0073] When the coating comprising silanol groups on its surface is an anti-reflective coating, the luminous reflection of an article coated with such an anti-reflective coating, noted Rv, is less than 2.5% per face, more preferably of less than 2% per face and even more preferably less than 1% per face of the article. In a more preferred embodiment, the article comprises a substrate, both main surfaces, which are coated with an anti-reflective coating according to the invention and has a total Rv value (accumulated reflection of both sides) less than 1.5% . The means for achieving the Rv values are well known from those skilled in the art. Petition 870190016216, of 02/18/2019, p. 11/25 16/49 [0074] In the present invention, the “light reflection factor” is as defined in the ISO 13666: 1998 standard, and is measured according to the ISO 8980-4 standard, which is to say that it is the average weight of the spectral reflectivity within the visible wavelength spectrum ranging from 380 to 780 nm. [0075] Before forming the precursor anti-fog coating on the coating comprising silanol groups on the surface thereof, for example, an anti-reflective coating, it is usual to subject the surface of such coating to a physical or chemical activation treatment intended to reinforce adhesion of the precursor of anti-fog coating. These treatments can be selected from those previously described to activate the coating comprising a silanol group on its surface. [0076] According to the invention, the coating comprising silanol groups on its surface is directly in contact with the precursor coating of an anti-fog coating, which will be described here below. [0077] As used herein, "a precursor to an anti-fog coating" is intended to mean a coating that, if a liquid solution containing a surfactant is applied to the surface of the same to form a film, represents an anti-fog coating within the meaning of the invention. The precursor coating system + surfactant-based film represents the anti-fog coating such as. [0078] The precursor coating to the anti-fog coating is a coating having a thickness less than or equal to 5 nm, preferably 4 nm or less, more preferably 3 nm or less and even more preferably 2 nm or less, having a angle of static contact with water of more than 10 o and less than 50 o , which is obtained through a permanent graft of at least one organosilane compound having a polyoxyalkylene group and at least one silicon atom having at least one hydrolyzable group. [0079] In one embodiment of the invention, the coating is deposited by applying a composition comprising a hydrolyzate of the organosilane compound Petition 870190016216, of 02/18/2019, p. 11/26 17/49 having a polyoxyalkylene group and at least one silicon atom carrying at least one hydrolyzable group. [0080] It is recommended to avoid any condensation of the hydrolyzed organosilane compounds in such a way that they keep silanol functions free as much as possible to react in order to facilitate the grafting of these compounds on the surface of the optical article and to limit the formation of siloxane prepolymers before of the graft. This is why the thickness of the deposited organosilane compound is so thin. [0081] It is therefore recommended to apply the composition relatively quickly after hydrolysis, typically within less than 2 hours, preferably less than 1 hour, more preferably less than 30 minutes after doing the hydrolysis (by adding typically acidic aqueous solution based in HCl). [0082] More preferably, the composition is applied less than 10 minutes, even more preferably less than 5 minutes and preferably less than 1 minute after having done the hydrolysis. [0083] It is preferred to conduct hydrolysis without a heat supplement, that is, typically at a temperature of 20 to 25 ° C. [0084] As a rule, the deposition of a few layers of nanometric thickness requires the use of very diluted compositions, with a very low dry matter content, which reduces the condensation kinetics. [0085] The organosilane compound used is capable, thanks to its reactive groups containing silicon, to establish a covalent bond with the silanol groups present on the surface of the coating where it is deposited. [0086] The organolysane compound of the invention comprises a polyoxyalkylene chain functionalized in only one termination or in both terminations thereof, preferably in only one termination, by a group comprising at least one silicon atom carrying at least one hydrolyzable group. This organosilane compound preferably comprises a silicon atom carrying at least two hydrolyzable groups, preferably three groups Petition 870190016216, of 02/18/2019, p. 11/276 18/49 hydrolyzable. Preferably, it does not comprise any urethane group. It is preferably a compound of the formula: R1YmSi (X) 3-m (I) in which Y groups, being the same or different, are organic monovalent groups linked to the silicon atom through a carbon atom, groups X, being the same or different, are group hydrolyzable, R 1 is a group comprising a polyoxyalkylene function, m is an integer equal to 0, 1 or 2. Preferably m = 0. The groups X are preferably selected from the alkoxy groups OR 3 , particularly C1-C4 alkoxy groups, acyloxy groups -OC (O) R 4 where R 4 is an alkyl radical, preferably a C1-C6 alkyl radical, preferably a methyl or ethyl, halogens such as Cl, Br and I or trimethylsilyloxy (CH3) 3SiO-, and combinations of these groups. Preferably, groups X are alkoxy groups, and particularly methoxy or ethoxy groups, and more preferably ethoxy groups. The group Y, present when m is not zero, is preferably a saturated or unsaturated hydrocarbon group, preferably a C1-C10 group and more preferably a C1-C4 group, for example, an alkyl group, such as a methyl group or an ethyl, a vinyl group, an aryl group, for example, an optionally substituted phenyl group, especially substituted by one or more C1-C4 alkyl groups. Preferably Y represents a methyl group. [0089] In a preferred embodiment, the compound of formula I comprises a trialcoxysilyl group such as a triethoxysilyl group or a trimethoxysilyl. The polyoxyalkylene group of the organosilane compound (group R 1 ) preferably comprises less than 80 carbon atoms, more preferably less than 60 carbon atoms, and even more preferably less than 50 carbon atoms. The group R 1 preferably satisfies the same conditions. [0091] The group R 1 generally corresponds to the formula -LR 2 · where L is a divalent group attached to the silicon atom of the compounds of formula I or II via a carbon atom, and R 2 is a group comprising a polyoxyalkylene group Petition 870190016216, of 02/18/2019, p. 11/28 19/49 linked to group L via an oxygen atom, this oxygen being included in group R 2 . Non-limiting examples of L groups include linear or branched groups, optionally alkyl, cycloalkylene, arylene, carbonyl, optionally substituted starch, or combinations of such groups such as cycloalkylene alkylene, biscicloalkylene, biscicloalkylene alkylene, arylene alkylene, bisphenylene, bisphenylene alkylene, alkylene starch groups, among which, for example, the CONH (CH2) 3 group, or -OCH2CH (OH) CH2- and -NHC (O) - groups. Preferred L groups are alkyl groups (preferably linear), preferably having 10 carbon atoms or less, more preferably 5 carbon atoms or less, for example, ethylene and propylene groups. Preferred groups R 2 comprise a polyoxyethylene (CH2CH2O) n- group, a polyoxypropylene group, or combinations of these groups. [0093] Preferred organosilanes of formula I are composed of the following formula II: Ym (X) 3-mSi (CH2) n- (L ') m- (OR) nO- (L) mR' (II) where R 'is a hydrogen atom, a linear or branched acyl or alkyl group, optionally substituted by one or more functional groups, and which may furthermore comprising one or more double bonds, R is a linear or branched alkylene group, for example, an ethylene group or a propylene, L 'and L ”are divalent groups, X, Y as defined above, n 'is an integer ranging from 1 to 10, preferably from 1 to 5, n is an integer ranging from 2 to 50, preferably from 5 to 30, more preferably from 5 to 15, m 'is 0 or 1, preferably 0, m ”is 0 or 1, preferably 0. [0094] The groups L 'and L' ', when present, can be selected from divalent groups previously described and preferably represented by the group -OCH2CH (OH) CH2- or the group -NHC (O) -. In this case, the groups -OCH2CH (OH) CH2or -NHC (O) - are linked to the adjacent groups (CH2) n · (with a group L ') and R' (with a group L '') through their atom oxygen (for the -OCH2CH (OH) CH2- group) or through its nitrogen atom (for the -NHC (O) - group). Petition 870190016216, of 02/18/2019, p. 11/29 20/49 [0095] In one embodiment, m = 0 and the hydrolyzable groups X represent a methoxy or ethoxy group. N 'is preferably 3. In another embodiment, R' represents an alkyl group having less than 5 carbon atoms, preferably a methyl group. R 'can also represent an aliphatic or aromatic acyl group, especially an acetyl group. [0096] Finally, R 'can represent a trialcoxysilylalkylene group or a trialogenosylylalkylene group such as a - (CH2) n''Si (R 5 ) 3 group where R 5 is a hydrolyzable group like the previously defined groups X and n''is an integer such as the integer n' previously defined. An example of such a group R 'is the group - (CH2) 3Si (OC2H5) 3. In this embodiment, the organosilane compound comprises two silicon atoms carrying at least one hydrolyzable group. [0097] In preferred embodiments, n is 3, or ranges from 6 to 9, from 9 to 12, from 21 to 24, or from 25 to 30, preferably from 6 to 9. [0098] To be mentioned as suitable compounds of formula II are, for example, 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane compounds of formulas CH3O- (CH2CH2O) 6-9- (CH2) 3Si (OCH3) 3 (III) and CH3O- (CH2CH2O) 9-12- (CH2) 3Si (OCH3) 3 (IV), marketed by Gelest, Inc. or ABCR, the compound of the formula CH3O (CH2CH2O) 3- (CH2) 3Si (OCH3) 3 ( VIII), compounds of the formula CH3O- (CH2CH2O) n (CH2) 3Si (OC2H5) 3 where n = 21-24, 2- [methoxy (polyethyleneoxy) propyl] trichlorosilanes, 2 [acetoxy (polyethyleneoxy) propyl] trimethoxysilane of the formula CH3C (O) O- (CH2CH2O) 6-9 (CH2) 3Si (OCH3) 3, 2- [acetoxy (polyethyleneoxy) propyl] triethoxysilane of formula CH3C (O) O (CH2CH2O) 6-9- (CH2) 3Si (OC2H5 ) 3, 2- [hydroxy (polyethyleneoxy) propyl] trimethoxysilane of formula HO- (CH2CH2O) 6-9- (CH2) 3Si (OCH3) 3, 2 [hydroxy (polyethyleneoxy) propyl] triethoxysilane of formula HO- (CH2CH2O) 6 -9 (CH2) 3Si (OC2H5) 3, compounds of formulas HO- (CH2CH2O) 8-12- (CH2) 3Si (OCH3) 3 and HO- (CH2CH2O) 8-12- (CH2) 3Si (OC2H5) 3, polypropylene-bis oxide ((3methyldimethoxysilyl) propyl], and compounds with two head siloxanes such as polyethylene-bis [(3-triethoxysilylpropoxy) -2-hydroxypropoxy] of formula (V), polyethylene-bis [(N, N'-triethoxysilylpropyl) -aminocarbonyl] of formula (VI) with n = 10-15 and polyethylene-bis (triethoxysilylpropyl) oxide of formula (VII): Petition 870190016216, of 02/18/2019, p. 11/30 21/49 OH, OCH-.raCEÍi-Ü-ÍCK CH. i ' CH. IJCm / l OH E y ^ ChjCHCEljO idiocy (V) I H , CO— (CHCHjO) —C CH. F 'CH-, E CH. (CH <O) 3 If (SAW) ÇCHJCHj CHiCHiÇ CH £ H Ό- CHjCH JCH ^ ICH ίΗΌ) --- CH, CH £ H ^ j- OCHJZHj CHjCHp 25-30 OCHJCH] (VII) [0099] Preferred compounds of formula II are [alkoxy (polyalkyleneoxy) alkyl] trialkoxysilanes or their trialogenated analogs (m = m '= m = 0, R' = alkoxy). [00100] Preferably, the organosilane compound of the invention will have no fluorine atom. Typically, the weight ratio of fluorine to the precursor coating of the anti-fog coating is less than 5%, preferably less than 1% by weight and more preferably 0%. [00101] Preferably, the molecular weight of the organosilane compound according to the invention varies from 400 to 4000 g / mol, preferably from 400 to 1500 g / mol, more preferably from 400 to 1200 g / mol, and even more preferably from 400 at 1000 g / mol. [00102] Of course it is possible to graft a mixture of compounds of formula I or II, for example, a mixture of compounds with different polyoxyalkylene RO chain lengths. [00103] In an embodiment of the invention, the precursor anti-fog coating comprises more than 80% by weight of an organosilane compound of Petition 870190016216, of 02/18/2019, p. 11/31 22/49 according to the invention, concerning the total weight of the precursor anti-fog coating, preferably more than 90%, more preferably more than 95% and more preferably more than 98%. In one embodiment, the precursor anti-fog coating consists of a layer of said organosilane compound. [00104] Preferably, the precursor anti-fog coating of the invention comprises less than 5% by weight of a metallic or metalloid oxide (for example, silica or alumina) relative to the total weight of the coating, more preferably it is free of any one. When the organosilane compound used to make the anti-fog coating is deposited under vacuum, preferably no metal oxide is co-evaporated, according to the method of co-evaporation of at least one organic compound and at least one inorganic compound described in the application EP 1324078. [00105] Preferably, the precursor coating of the anti-fog coating does not comprise any cross-linking agent, which means that it is preferably not formed from a composition comprising a cross-linking agent, for example, tetraethoxysilane. [00106] The precursor of the anti-fog coating of the invention has a static contact angle with water of more than 10 o and less than 50 o , preferably less than or equal to 45 o , more preferably <40 °, even more preferably <30 ° and more preferably <25 °. The contact angle preferably ranges from 15 ° to 40 °, more preferably from 20 ° to 30 °. [00107] The deposition of the organosilane compound on the surface of the coating comprising silanol groups can be carried out according to usual procedures, preferably by deposition of the gas phase or deposition of the liquid phase, more preferably in the gas phase, by vacuum evaporation. [00108] When the graft is carried out in the gas phase, for example, by evaporation under vacuum, it can be followed, if necessary, with a step to remove the excess of the organosilane compound deposited in order to retain only the organosilane compound that is actually grafted on the surface of the coating containing silanol group. Un grafted molecules are then Petition 870190016216, of 02/18/2019, p. 11/32 23/49 removed. Such a removal step must be especially done when the thickness of the precursor of the anti-fog coating initially deposited is greater than 5 nm. [00109] However this step to remove excess organosilane compound can be omitted in some cases, since it is possible to deposit the organosilane compound in order to form a grafted layer, that is to say once it ensures that the deposited thickness does not exceed a few nanometers. Adjusting the disposal parameters to obtain such thickness belongs to the ordinary competence of anyone skilled in the art. [00110] However, it is preferred to form the precursor coating of the anti-fog coating by depositing some excess organosilane compound on the surface of the coating comprising silanol groups and thus removing the excess of this deposited but not grafted compound. In fact, the inventors have observed that when a layer of grafted organosilane compound is directly formed with a thickness less than or equal to 5 nm, which does not require any removal of the excess organosilane compound, it is sometimes possible to obtain a precursor coating from a anti-fog coating, the surface of which does not have sufficient affinity for a liquid solution comprising at least one surfactant, which can lead to a coating not having the desired anti-fog properties. [00111] Surprisingly, it is not observed when the organosilane compound is deposited in excess, as previously indicated, and that excess is removed later. The actual physical thickness of the organosilane compound layer deposited in excess is preferably less than or equal to 20 nm. [00112] Removal of the organosilane compound deposited in excess can be done by washing (wet process) using, for example, a solution based on soapy water and / or by drying (dry process). Preferably, the removal step comprises a washing operation followed by a drying operation. Petition 870190016216, of 02/18/2019, p. 11/33 24/49 [00113] Preferably, the washing operation is carried out by cleaning the article with some soapy water (including a surfactant) using a sponge. Then a washing operation is performed with deionized water, and optionally, the lenses are then subjected to a drying operation for typically less than 20 seconds, preferably 5 to 20 seconds, using an alcohol-impregnated CEMOI® or Selvith® fabric , typically isopropyl alcohol. Another washing operation with deionized water can then be repeated, then a drying operation with a drying fabric. All of these steps can be performed manually or be partially or complemented automatically. [00114] The step to remove excess organosilane compound leads to a layer of organosilane compound having a thickness of 5 nm or less. The organosilane compound deposited on the surface of the optical article then forms a monomolecular or quasi-monomolecular layer. [00115] The organosilane compound can be previously dissolved in a solvent before being evaporated, for better control of the evaporation rate and the disposal rate. The thickness of the film can be controlled in this way thanks to this dissolution and by adjusting the amount of the solution to be evaporated. [00116] When the graft is performed using a wet process, for example, by immersion or spiral coating, it is generally not necessary to do a step of removing the excess deposited organosilane compound. [00117] The precursor coating of the anti-fog coating according to the invention has a low asparity. Typically, for an organosilane compound deposited by the vapor phase, the roughness Ra is less than 2 nm, typically around 1 nm. [00118] Ra (nm) is the average roughness of the measured surface: LyLx Ra = γ-Γ- · JJ | f (xy) dx-dy LxL yoo [00119] Lx and Ly are the sizes of the measured surface, f (x, y) is the surface in the central plane. Petition 870190016216, of 02/18/2019, p. 11/36 [00120] A temporary anti-fog coating according to the invention is obtained by depositing a film of a liquid solution comprising at least one surfactant on the surface of the precursor coating of the anti-fog coating. [00121] This solution provides the glass with a temporary anti-fog protection by creating a uniform layer on its surface that helps to disperse the water droplets on the glass surface so that they do not form any visible mist. [00122] Applying the surfactant solution can be done by any known method, especially by immersion or spiral coating. [00123] The surfactant solution is preferably applied by depositing a drop of this solution on the surface of the precursor of the anti-fog coating, and then dispersing it to cover the entire precursor coating. [00124] The applied surfactant solution is generally an aqueous solution, preferably comprising 0.5 to 10%, more preferably 2 to 8% by weight of a surfactant. A commercially available cleaning solution is advantageously used, which comprises a surfactant and becomes a spray or small tissue. [00125] A wide variety of surfactants can be used. These surfactants can be ionic (cationic, anionic or amphoteric) or non-ionic surfactants, preferably non-ionic or anionic surfactants. However, a mixture of surfactants belonging to these various categories can be contemplated. These surfactants for most of these are commercially available. [00126] Preferably, a surfactant is used which comprises poly (oxyalkylene) groups. [00127] Suitable examples of non-ionic surfactants for use in the present invention include poly (alkyleneoxy) alkyl ethers, especially poly (ethyleneoxy) alkylethers, marketed, for example, by the ICI company under the trademark BRIJ®, poly (alkyleneoxy fatty alcohols) ) alkyl amines, poly (alkyleneoxy) alkyl amides, Petition 870190016216, of 02/18/2019, p. 11/35 26/49 polyethoxylated, polypropoxylated or polyglycerolated, polyethoxylated, polypropoxylated or polyglycerolated alpha-diols, polyethoxylated, polypropoxylated or polyglycerolated fatty acids and polyethoxylated, polypropoxylated or polyglycerolated fatty acids, for example, all with a chain, including a chain, for example, with a chain containing, for example, 18 carbon atoms, where the number of ethylene oxide or propylene oxide units can especially vary from 2 to 50 and where the number of glycerol fractions can especially vary from 2 to 30, acetylene ethoxylated diols, compounds of the copolymer type block comprising same time of hydrophilic and hydrophobic blocks (for example, polyoxyethylene and polyoxypropylene blocks, respectively), copolymers of poly (oxyethylene) and poly (dimethylsiloxane) and surfactants incorporating a sorbitan group. [00128] Preferred anionic surfactants are those comprising a sulfonic acid group, among which to be mentioned are alkylsulfosuccinates, alkylethersulfosuccinates, alkylamidesulfosuccinates, alkylsulfosuccinamates, dibasic salts of polyoxyethylene alkyl sulfosuccinic acids, sulfasic acid, dibasic salts hemi-ester salts of sulfosuccinic acid, alkylsulphates and aryl sulphates such as sodium dodecylbenzene sulphonate and sodium dodecyl sulphate, ethoxylated fatty alcohol sulphate, alkylethersulfates, alkylamidoethersulfates, alkylsulfonates, alkylsulfonates, alkylsulfonates, alkylsulfonates, alkylsulfonates secondary alcohol, polyoxyalkylated carboxylic acid ethers, monoglyceride sulfates, polyoxyethylene sulfuric acid alkyl salts, sulfuric acid ester salts, N-acyltaurates such as Nacylmethyltau salts rin, hydroxyalkane salts of monosulfonic acid or alkene monosulfonates, the alkyl and acyl radical of all such compounds preferably comprising 12 to 20 carbon atoms and the optional oxyalkylene group of these compounds preferably comprising 2 to 50 monomer units. These anionic surfactants and many others to be used in the present application are described in application EP 1418211 and in US patent 5,997,621. Petition 870190016216, of 02/18/2019, p. 36/116 27/49 [00129] Suitable examples of cationic surfactants for use in the present invention include primary, secondary or tertiary grease amine salts, optionally polyoxyalkylenated quaternary ammonium salts such as tetraalkylammonium, alkylamidoalkyltriakylammonium, trialkylbenzylammonium, trialkylethylhydroxyalkylhydroxyalkylhydroxyalkylhydroxyalkylhydroxyalkylhydroxy , imidazoline derivatives or amine oxides of cationic nature. [00130] In one embodiment, the surfactant used comprises a fluorinated surfactant. In this case, those that will preferably be used comprise at least one fluoroquila or polyfluoroalkyl group and more preferably those that comprise at least one perfluoroquila group. [00131] The Clarity Defog it® solution from Nanofilm is a commercially available surfactant solution that provides anti-fog properties. [00132] Instead of a surfactant solution, it is possible to use hydrophilic compounds, more particularly compounds having no active surface properties comprising at least one hydrophilic group, preferably a poly (oxyalkylene) group, but surfactant solutions are preferred and give better anti-inflammatory results. - fogging solutions based on non-surfactant hydrophilic compounds. The anti-fog coating of the invention preferably has a static contact angle with water less than or equal to 10 o , more preferably less than or equal to 5 o . [00133] An immediately operational anti-fog coating is obtained as soon as the surfactant composition is applied, which represents one of the main advantages of the invention. Therefore, it is not necessary to apply a surfactant solution many times to achieve the anti-fog effect, as is the case with products of the prior art. [00134] In addition, the anti-fog effect provided by the anti-fog coating is long-lasting, as long as it lasts for a period of time ranging from several days to several weeks, which is a significant improvement as compared to anti-fog coatings known. This durability is Petition 870190016216, of 02/18/2019, p. 37/116 28/49 tested with mechanical stresses corresponding to repeated drying operations, in a procedure described in the experimental section. [00135] The anti-fog coating is temporarily but easily renewable, since only a new surfactant application has to be made when there are no more sufficient surfactant molecules adsorbed on the surface of the anti-fog coating precursor. The latter therefore remains "active" in all circumstances. [00136] The optical article according to the invention has no anti-fog coating, particularly no anti-fog coating based on fluorinated silanes, yet it is found to have satisfactory cleanability. Its ease of removing traces of grease is not as good as that of a fluorinated anti-fog coating, but it is better than that of a revealed anti-reflective coating, that is to say free of any anti-fog coating. [00137] However, the ease of application of the temporary anti-fog products in the precursor of the anti-fog coating according to the invention is better than in the fluorinated anti-fog coatings that are generally used. In addition, the durability of the anti-fog effect obtained thanks to a temporary anti-fog product is greater in the context of the invention than when this anti-fog product is applied to the anti-fog coating. [00138] The present invention also relates to a method for making an optical article, preferably a lens for glasses, as defined above, comprising the steps of: a) providing a substrate provided with a coating comprising a silanol group on its surface, b) depositing in said coating, preferably by vacuum evaporation, at least one organosilane compound having a polyoxyalkylene group and at least one silicon atom carrying at least one hydrolyzable group, in order to obtain a layer of grafted organosilane compound having a smaller thickness than or equal to 5 nm, by optionally removing excess organosilane compound that has been deposited but not grafted Petition 870190016216, of 02/18/2019, p. 38/116 29/49 on the surface of the coating comprising silanol groups, in order to obtain a static contact angle with water of more than 10 o and less than 50 o . [00139] This method may further comprise an additional step for depositing a film of a liquid solution comprising at least one surfactant on the surface of the layer formed in step b), then giving access to an anti-fog coating. [00140] Preferably, the precursor coating of the anti-fog coating is not subjected to extended heating prior to the application of said liquid solution comprising at least one surfactant. Heating the precursor coating to 50-60 ° C for several hours can damage the optical article. In addition, upon deposition of the anti-fog precursor coating, it is not necessary to heat the optical article. [00141] The present invention finally relates to an optical article, preferably a lens for glasses, comprising a substrate provided with a coating comprising silanol groups on the surface thereof, a part of the surface of said coating comprising silanol groups on the surface thereof directly in contact with a precursor coating of the anti-fog coating as previously defined, and another part of the surface of said coating comprising silanol groups on the surface thereof, preferably the residue of its surface, being in direct contact with, and adhering to a coating hydrophobic and / or oleophobic. These parts can be continuous or decontinuous. [00142] Such an optical article can especially be used as a demonstrator to show anti-fog properties, after application of the surface to it of a liquid solution comprising at least one surfactant and / or a hydrophilic compound with no active properties on the surface such as previously defined, then by submitting the article to mist-generating conditions (breathing, cooling, boiling water vapor ...) or by subjecting its surface to one or more drying operations before being exposed to mist-generating conditions. Petition 870190016216, of 02/18/2019, p. 39/116 30/49 [00143] The optical article darkens on this part of the surface covered with the hydrophobic and / or oleophobic coating and remains transparent in the area comprising the anti-fog coating. [00144] Hydrophobic and / or oleophobic coatings, or anti-fog surface coatings that may be suitably used in this optical article are especially described in application WO 2010/055261. They differ naturally from the anti-fog coatings of the invention. [00145] The hydrophobic and / or oleophobic coatings used preferably have a surface energy less than or equal to 14 mJ / m 2 , preferably less than or equal to 12 mJ / m 2 , according to the Owens Wendt method described in the article referred to in WO2010 / 055261. [00146] Although the present invention is not limited to this method, such an optical article can be formed by the use of an optical article provided with a coating comprising silanol groups on the surface thereof, at least part of the surface of said coating being directly coated with a hydrophobic and / or oleophobic coating, by submitting at least a part of this hydrophobic and / or oleophobic coating for a removal treatment, in order to reveal the base coating comprising silanol groups on its surface, then it can deposit on said revealed layers of at least one organosilane compound according to the invention, in order to form a precursor coating of anti-fog coating as previously described. [00147] Any chemical or physical means to remove part of the hydrophobic and / or oleophobic coating can be used. It will be preferred to bombard the coating with argon ions by means of an ionic weapon, but plama-mediated treatment under vacuum, corona discharge, electron beam bombardment or ultraviolet treatment can also be suitably employed, under conditions that will be easily determined by someone skilled in the art. If the optical article comprises an electrically conductive layer, especially a conductive layer providing anti-static properties in a Petition 870190016216, of 02/18/2019, p. 40/116 31/49 anti-reflective coating, an ionic bubbling will preferably be used to avoid any damage to the article. To limit the removal of the treatment to only a part of the hydrophobic and / or oleophobic coating, a protective medium can be used such as a mask or any other suitable method, placed on the surface of the article to be treated or optionally sandwiched between the source and the surface to be treated in the event of treatments mediated by energetic species such as ions, photons or electrons. [00148] Use of masks in optics is usual, and is especially described in US patent 5,792,537. [00149] As an alternative, the previously mentioned optical article can be manufactured from a lens coated with a coating according to the invention, the surface comprising silanol group, of which it is partially developed according to the previously described method, and then the hydrophobic and / or oleophobic coating is deposited on said revealed surface. [00150] The following examples illustrate the invention in an even more detailed non-limiting form. EXAMPLES 1. MATERIALS AND OPTICAL ITEMS USED [00151] Silica is used in the form of granules provided by the company Optron Inc. The organosilane compound used in the examples to form the anti-fog precursor coating is 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane comprising 6 to 9 ethylene oxide units (examples 1-4, 6, 7), of formula (III) and with a molecular weight of 450-600 g / mol (CAS No .: 65994-07-2. Ref: SIM6492 .7, provided by the company Gelest, Inc.), or 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane comprising 3 ethylene oxide units (example 5) of formula (VIII). [00152] The comparative compounds used in comparative examples C4 to C7 are 2- [methoxy (polyethyleneoxy) propyl] triethoxysilane comprising 45 ethylene oxide units, of the formula CH3O- (CH2CH2O) 45- (CH2) 3Si (OC2H5) 3 ( IX), provided by the company Interchim, or HO (CH2CH2O) 45CONH (CH2) 3Si (OCH2CH3) 3 (X) compound, Petition 870190016216, of 02/18/2019, p. 41/116 32/49 provided by the ABCR company (CAS No .: 37251-86-8). The compound of formula (X) is the compound used in comparative example 3 of JP application 2005-281143. [00153] Unless otherwise specified, the lenses used in the examples of the invention comprise a polyurethane lens substrate (thermoset PTU marketed by Mitsui Toatsu Chemicals), with a refractive index of 1.60, 65 mm in diameter, force of -2.00 diopters and thickness of 1.2 mm. [00154] These glasses are treated on both sides according to the methods described here below, the concave face being treated before the convex face. [00155] This substrate is coated with an abrasion resistant and scratch resistant coating with a refractive index of 1.60, as well as with a monolayer anti-refractive coating of about 100 nm thick and with a refractive index of 1, 40, obtained using a sol-gel method (pointed anti-reflective coating X) (obtained by depositing an alkoxysilane-based composition comprising empty colloidal particles, heated after depositing for 3 hours at 100 o C), or with a commercial anti-reflective coating of four layers ZrO2 / SiO2 / ZrO2 / SiO2 (pointed anti-reflective coating Z) deposited in the abrasion resistant coating by vacuum evaporation of the materials in order to which they are mentioned (respective layer thicknesses: 27, 21, 80 and 81 nm). [00156] Before depositing a plasma-assisted surface, the lenses comprising the anti-reflective coating X are subjected to a plasma-assisted surface activator treatment (0.2 mBar, 200 mL O2 / min, 2 min at 500 W then 5 min at 0 W). [00157] The lenses comprising the anti-reflective coating Z are subjected to any activating treatment. [00158] In examples 4-6, the lenses used comprise a substrate lens in an ORMA® material comprising an impact resistant primer based on polyurethane with a thickness of about 1 micron, provided with a Petition 870190016216, of 02/18/2019, p. 42/116 33/49 abrasion resistant coating with a thickness of about 3 microns by depositing and curing a composition as defined in example 3 of patent EP 614957, coated in turn (except example 4) with a five-layer anti-reflective coating ZrO2 / SiO2 / ZrO2 / ITO / SiO2 (pointed anti-reflective Y coating) deposited on the vacuum-resistant abrasion-resistant coating of the materials in the order they are mentioned (respective layer thicknesses: 29, 23, 68, 7 and 85 nm ). An ITO layer is an electrically conductive layer of tin oxide (In2O3: Sn). [00159] Before depositing the anti-fog coating precursor, the lenses comprising the abrasion resistant coating are subjected to an activating surface treatment, which consists of doing an ion bombardment with a rare gas or oxygen, in this case a gas rare is argon, under vacuum, at a pressure of typically 3.5.10 -5 mbar. [00160] In the examples, the anti-reflective coating is not subjected to any activating treatment before depositing the anti-fog precursor coating. [00161] The precursor anti-fog coating has been deposited according to two different methods: 2. PREPARATION OF PRECURSING ANTI-SMOOTH COATINGS A) DEPOSITION OF THE PRECURSOR ANTI-SMOOTHING COATING USING A WET PROCESS (EXAMPLE 1) [00162] 1 g of formula III siloxane compound is diluted in 9 g of isopropanol. 4 g of the resulting solution is then diluted with 145 g of isopropanol. The solution is stirred for 2 minutes at room temperature, then slightly acidified by the addition of 0.2 g of 0.1 N HCl and finally deposited in a spiral coating (3000 rpm / 30 sec / acceleration: 2000 rpm / s; 50% moisture) in the anti-reflective coating X of a lens, the surface of which has been activated as indicated above. The anti-fog precursor coating is then heated for 15 min at 75 ° C then for 3 h at 100 ° C. At the end of this step, its thickness, assessed through an ellipsometric analysis, is 3 to 5 nm. Since the siloxane compound of Petition 870190016216, of 02/18/2019, p. 43/116 34/49 formula III has not been deposited in excess, no drying or washing removal steps have been taken. B) STEAM DEPOSITION OF THE PRECURSOR ANTI-DAMAGE COAT (EXAMPLES 2-6) [00163] In example 2, deposition is performed on the anti-reflective coating Z of a lens by vacuum evaporation using a heating source based on the Joule effect. 150 pL of the siloxane compound of formula III is impregnated in a nickel foam inside a copper capsule (deposition thickness: 10 nm, deposition rate: 0.25 nm / s, pressure when deposition starts: 2.10 -5 mBar ). [00164] Once the evaporation is complete, the surface of each lens is rubbed with a dry Cémoi® tissue until the excess siloxane compound of formula III deposited is removed. A homogeneous coating is then obtained. The anti-fog coating of example 2 has a thickness of 1-3 nm. [00165] The Cémoi® fabric is a fabric provided by the supplier Facol under the reference Microfiber M8405 30x40. [00166] In example 4, deposition is carried out on the abrasion resistant coating of a lens by vacuum evaporation using a heating source based on the Joule effect. The siloxane compound and this capsule are deposited on a heating support in a tantalum conductor. The evaporator device is a SATIS 1200 DLF apparatus. The evaporation pressure of the siloxane compound of formula III generally ranges from 5.10 -6 to 8.10 -6 mbar. Once evaporation is complete, the surface of each lens is washed with some soapy water, optionally isopropyl alcohol, then deionized water and rubbed with a dry Cémoi® fabric so that the excess deposited formula III siloxane is removed . [00167] In examples 5-6, deposition is performed on the anti-reflective coating Y of a lens by evaporation under vacuum according to a protocol similar to example 4, using an organosilane of formula III or VIII, with an evaporation rate 0.3 nm / s program. A layer about 12 nm thick is Petition 870190016216, of 02/18/2019, p. 44/116 35/49 obtained (before removing the excess siloxane compound), which is optionally heated for 1 h at 60 ° C (only for examples C6 and C7). The excess siloxane compound is then removed as described in example 4. C) COMPARATIVE EXAMPLES [00168] The lenses of comparative example C1 differ from those of example 1 in that they do not comprise any precursor anti-fog coating. [00169] The lenses of comparative example C2 differ from those of example 2 in that they do not comprise any precursor anti-fog coating. [00170] The lenses of comparative example C3 differ from those of comparative example C2 in which a 2-3 nm thick anti-fog coating is formed in the anti-reflective coating by vacuum evaporation from the OPTOOL DSX® composition, marketed by Daikin Industries (fluorinated resin comprising perfluorpropylene groups corresponding to the formula given in US patent 6,183,872). [00171] The lenses of comparative examples C4 to C7 have a precursor coating to the anti-fog coating formed from an organosilane compound which is not in accordance with the present invention, because of a polyoxyalkylene group comprising more than 80 carbon atoms . D) DEPOSITION OF A LIQUID SOLUTION CONTAINING SURFACE (TEMPORARY ANTI-SMOOTHING SOLUTION) [00172] The articles of examples 1A, 2A, C1A-C7A, 4A, 5An and 6A have been obtained by applying the surfaces of the articles of examples 1, respectively, respectively 2, C1-C3 and 4 only once of the Clarity® Defog It solution, comprising surfactants (polyethylene glycols, in solution in isopropanol), sold by the company Nanofilm, simply referred to as “Defog It” here below. It can be applied to the lenses using a “Defog It” trademark fabric comprising this solution, or by directly dispersing the “Defog It” anti-fog liquid. E) TESTS AND RESULTS Petition 870190016216, of 02/18/2019, p. 45/116 36/49 [00173] The performances of the prepared optical articles and their constitution are summarized in Tables 1, 2 and in the paragraphs below. Table 1 Example 1 / 1A 2 / 2A C1 / C1A C2 / C2A C3 / C3A Anti-reflective coating X Z X Z Z Anti-fog precursor coating Yes Yes No No No Coating deposition methodanti-fog precursor ProcessMoist Evaporation - - - Anti-dirt coating No No No No Yes Angle of static contact with water (°)before applying Defog it 25(ex. 1) 25(ex. 2) 102(C1) 42(C2) 118(C3) Cleanability (index /10)before applyingDefog it 5(ex. 1) 3(ex. 2) 0(C1) 2(C2) 9(C3) Breathing Test N(e.g. 1, 1A) N(ex. 2. 2A) Yes (C1)N (C1A) Yes (C2)N (C2A) Yes (C3)N (C3A) Durability over time with anti-fog effect afterDefog It solution application > 15 days > 15 days <3 days <24h <24h Application efficiency of Defog It fabric (number of applications *) 1 1 3 > 5 5 Efficiency of the application of the Defog It solution (number of applications *) 1 1 > 3 > 3 > 3 Refrigerator test 1A (0) 2A (0)C2 (2)Hot steam test 2A (0) 2A (0) C1 (2)C1A (2) C2 (2)C2A (2) [00174] * From the lenses comprising the precursor anti-fog coating (with no previous application of Defog it in it). Petition 870190016216, of 02/18/2019, p. 46/116 37/49 [00175] The lenses of example 4A have anti-fog properties comparable to those of examples 1A and 2A. E1) EVALUATION OF ANTI-SMOOTH PROPERTIES [00176] Anti-fog properties can be evaluated according to three methods: the “breath test” (qualitative test that does not use any visual acuity measurement), the “vapor test hot ”and the“ refrigerator test ”. Breath and refrigerator tests are considered as low fog stress generators. The hot steam test is considered to be a high fog stress generator. BREATH TEST [00177] For this test, the tester places the lenses to be evaluated at a distance of about 2 cm from your mouth. The checker for 3 seconds blows your breath on the exposed surface of the glass. The tester can visually observe the presence or absence of a condensation fog / distortion. Yes. Presence of fog N. No fog: such a lens is considered to have anti-fog properties at the end of the breath test, that is, it inhibits the fog effect resulting from the fog (but does not necessarily represent an anti-fog glass within the meaning of the invention. , because it can present visual distortion leading to visual acuity <6/10 only). HOT STEAM TEST [00178] Before testing, the glasses are placed for 24 hours in an environment of regulated temperature (20-25 ° C) and under 50% humidity. [00179] For the test, the glasses are placed for 15 seconds above a heated container comprising water at 55 ° C. Immediately afterwards, a visual acuity scale at a distance of 5 m is observed through the glasses tested. The tester assesses visual acuity as a function of time and according to the following criteria: O. No fog, no visual distortion (visual acuity = 10/10) 1. Mist and / or visual distortion allowing visual acuity> 6/10 Petition 870190016216, of 02/18/2019, p. 47/116 38/49 2. Mist and / or visual distortion allowing visual acuity <6/10 [00180] In practical terms, to obtain the index 0 or 1, a user having a vision of 10/10 and having placed the glasses in front of their eyes must be able to distinguish the orientation of the letters “E” in line 6/10 of the Snellen optotype table placed at a distance of 5 meters. [00181] This test makes it possible to stimulate common living conditions where a user leans his face to a cup of tea / coffee or in a pot full of boiling water. REFRIGERATOR TEST [00182] For this test, the lenses are placed in sealed boxes containing a desiccant (silica gel). The boxes in turn are placed in a refrigerator at 4 o C for at least 24 h. After this period of time, the boxes are removed from the refrigerator and the glasses are immediately tested. They are then placed in an atmosphere of 45-50% humidity and at 20-25 ° C. A visual acuity scale located at a distance of 4 m is observed through the glass. The observer evaluates visual acuity as a function of time and according to the same criteria as the hot steam test (indexes 0, 1 or 2). [00183] This test makes it possible to stimulate common living conditions where a user leaves a cold, dry place and enters a hot and humid room. TEST RESULTS FOR EVALUATING THE ANTI-DAMAGE PROPERTIES [00184] The results of the hot steam test are given in figure 1. It can be seen that only the glasses of examples 1A and 2A represent anti-fog glasses within the meaning of the invention. In addition, they are immediately operational. Glasses that are devoid of any hydrophilic surface coating (examples C2 and C3) and glasses provided with a precursor anti-fog coating do not represent anti-fog glasses within the meaning of the invention, because they create a visual distortion that does not allow to achieve a visual acuity> 6/10 after being exposed to hot steam. However, the glasses Petition 870190016216, of 02/18/2019, p. 48/116 39/49 of examples 1 and 2 have anti-fog properties in the context of the breath test. [00185] All non-fog glasses end after a time leading to a visual acuity of 10/10, once the water vapor has evaporated. E2) EVALUATION OF DIRT REMOVAL FACILITY PROPERTIES (CLEANING) [00186] The ease of removing dirt (cleanability) from the surface of lenses, without depositing a liquid solution containing surfactant has been evaluated by depositing on the surface of glasses a finger mark by means of a stencil and by smearing this mark with a fabric ref. TWILLX 1622. The glasses are observed on a dark background and classified by an appraiser from the easiest to clean to the least easy to clean. This rating is associated with an index given by the evaluator ranging from 0, difficult to clean to 10, very easy to clean. This test makes it possible to stimulate common living conditions where a wearer wipes the fingerprints that are present on his glasses with a tissue to rub. [00187] The tested glasses and the results are given in table 1 and demonstrate that the glass that is easier to clean is naturally the one provided with a fluorinated anti-fog coating (example C3). The glasses comprising an anti-fog precursor coating according to the invention (example 1 and 2) are easier to clean than those that have none, or similar to those (examples C1 and C2), having an uncoated anti-reflective coating. E3) EVALUATION OF THE EFFICIENCY OF THE APPLICATION OF TEMPORARY ANTI-DAMAGE PRODUCTS [00188] Successive depositions of a temporary anti-fog product (solution or smear) are carried out in tested glasses (Ex 1, 2, 4, C1, C2, C3) until no fog nor distortion are generated with the hot steam test described above (perfect anti-fog effect). The expected effect is a level of performance leading to glasses showing neither fog nor distortion. The number of Petition 870190016216, of 02/18/2019, p. 49/116 40/49 applications that are required to achieve this level of performance are given in table 1. [00189] Use of the Defog It fabric: The glasses are rubbed with the fabric by making spiral movements from the center to the periphery with the Defog It fabric on each face. This corresponds to an application. The number of applications has been limited to 5. [00190] Use of the Defog It solution: Two drops of the Defog It solution are deposited on each side of the glass and are dried by making spiral movements from the center of the periphery with a Cémoi® drying fabric. This corresponds to an application. The number of applications has been limited to 3. [00191] The results are given in table 1 and allow us to point out that a single application of temporary anti-fog product is required in a precursor coating of the anti-fog coating to the invention to obtain an anti-fog coating, which simplifies the use of solutions temporary anti-fog. The other surfaces require multiple applications of the anti-fog solution to possibly hope to achieve the same level of anti-fog performance. Thanks to the present invention, the surface of the coating comprising silanol groups has somehow been made compatible with a surfactant thanks to the grafting of an organosilane compound according to the invention. [00192] The inventors think that such ease of application results not only from the hydrophilic properties of the surfaces of anti-fog precursor coatings, but also from the chemical nature of the formula III organosilane compound. E4) DURABILITY OF THE ANTI-SMOOTH EFFECT AFTER A MECHANICAL STRESS (AFTER APPLICATION OF THE DEFOG IT SOLUTION) [00193] The durability for mechanical stress (smear) of the anti-fog effect acquired by a temporary anti-fog solution applied using a Defog It fabric has been evaluated as follows. Petition 870190016216, of 02/18/2019, p. 50/116 41/49 [00194] The deposition of the temporary anti-fog solution is carried out as many times as necessary so that, in an initial moment, all lenses can be considered as anti-fog lenses at the end of the hot steam test described above . The lenses are then rubbed with a Cémoi® drying cloth and again subjected to the hot steam test. (The glasses are rubbed when the water film caused by the mist has disappeared. If the glasses are rubbed while the water film is still present, the anti-fog solution is partially removed). [00195] A smear operation corresponds to two very marked rotations of a Cémoi® drying fabric on the lens surface. The indices (0, 1 or 2) correspond to the mist level at the end of the second steam test, after the corresponding number of smear operations. [00196] The results of the durability test are given in table 2. Number of smear operations Example 1Anti-indexfoggy Example C1Anti-indexfoggy Example C3Anti-indexfoggy 1 0 0 2 2 0 03 0 04 0 05 0 16 0 210 1 [00197] On a hydrophobic surface (example C3), a smear operation is sufficient to completely change the anti-fog properties provided by the temporary solution Defog It. [00198] A more hydrophobic surface (surface of the anti-reflective coating of example C1), 5 smear operations are required to see an early Petition 870190016216, of 02/18/2019, p. 51/116 42/49 deterioration of the anti-fog properties provided by the temporary solution Defog It. [00199] On a surface of an anti-fog coating according to the invention, 10 smear operations are required to see an early deterioration of the anti-fog properties provided by the temporary solution Defog It. [00200] An anti-fog coating according to the invention then significantly improves the durability of the anti-fog property provided by a temporary anti-fog solution for a mechanical smear operation. E5) DURABILITY OVER THE TIME OF THE ANTI-SMOOTH EFFECT (AFTER APPLICATION OF THE DEFOG IT SOLUTION) [00201] The durability over time of the anti-fog effect after deposition of the temporary Defog It solution has been evaluated, this time with no stress on the glass after deposition. The glass is stored at room temperature and humidity (~ 20-25 ° C, relative humidity ~ 30%). The deposition of the anti-fog solution is performed as many times as necessary so that, at the beginning, all glasses can be considered as anti-fog glasses at the end of the breath test. The evolution of the anti-fog effect is then regularly tested through the breath test. Table 1 gives the time after applying the anti-fog solution after which the glasses are not considered to have more anti-fog properties at the end of the breath test. Tests have been stopped after 15 days. [00202] It can be noted that the surfaces of the anti-fog precursor coating according to the invention leads to a durability of the anti-fog effect provided by the temporary solution for more than 15 days, which is much better than the other surfaces tested. The inventors think that this durability results not only from the hydrophilic properties of the surfaces of anti-fog precursor coatings, but also from the chemical nature of the organosilane compound of formula III. Petition 870190016216, of 02/18/2019, p. 11/116 43/49 E6) CONTACT ANGLE OF THE PRECURSOR COATING OF THE ANTI-SMOOTHING COAT (TABLES 1 AND 4) [00203] The measurements are carried out on a Digidrop goniometer from the company GBX, based on samples in which the organosilane compound deposited in excess has been removed. 4 pL of water is automatically deposited on the surface of the sample to be analyzed, so the contact angle is measured. The results are given in table 1. E7) ANTI-REFLECTION PROPERTIES [00204] The reflection spectrum of the glasses has been examined before and after the deposition of the temporary Defog It solution. Each lens has anti-fog properties at the end of the breath test after applying this solution. [00205] Table 3 here below shows the variations observed on the reflection spectrum after deposition of the temporary Defog It solution. ExampleRv%Before depositing the solutionDefog it Rv%After depositing the solutionDefog it ARv% 1 / 1A 1.45 1.92 0.47 2 / 2A 0.72 0.44 -0.28 C2 / C2A 0.77 0.48 -0.29 C3 / C3A 0.50 0.46 -0.04 [00206] The articles resulting from a modification of its surface by grafting the organosilane of formula II (before depositing the active solution on the surface) retain anti-reflective properties corresponding to the criteria of the ophthalmic industry. 4. EXAMPLE 3 Petition 870190016216, of 02/18/2019, p. 53/116 44/49 [00207] In this example, a silicon substrate (wafer) has been used instead of a lens to more accurately measure the thickness of the deposited layers. [00208] The optical article used in this example comprises a silicon substrate coated with a 50 nm thick silica-based layer applied by vapor deposition (programmed thickness: 140 nm, programmed deposition rate: 3 nm / s). This silica-based layer has a 33 ° static contact angle of water 3 days after deposition, evolving to 43 ° within 2-3 months. [00209] The anti-fog precursor coating is deposited on this silica-based layer by chemical vapor deposition of the siloxane compound of formula III under the same conditions as in example 2, which takes before removing excess organosilane compound to a thick layer 10 nm with a static contact angle of 10 o at t = 3 days. [00210] Once the evaporation is complete, the surface of the article is washed with some soapy water and dried with a dry Cémoi® fabric. A coating is then obtained, having a thickness of 1-3 nm and a homogeneous surface, and having a static contact angle with water of 39 o . [00211] After application of a temporary solution "Defog It" comprising a surfactant, an anti-fog coating is obtained having a static contact angle with water of less than 5 it. [00212] The durability of the anti-fog coating has been evaluated by making 50 dry drying operations on the surface of the optical article using a Cémoi drying fabric (50 front and back motions). After this operation, the article has a static contact angle with water of less than 3 °, which demonstrates that the temporary solution “Defog It” is still present on its surface. [00213] In this example, the thickness has been analyzed through mono-wavelength ellipsometry considering that the global refractive index for the precursor layer of silica / anti-fog bilayer is 1.45. Petition 870190016216, of 02/18/2019, p. 54/116 45/49 5. EXAMPLES 5-6 AND COMPARATIVE EXAMPLES C4-C7: TESTS AND RESULTS [00214] The performances of the optical articles prepared in these examples and their composition are summarized in table 4 and in the paragraphs below. TABLE 4 Example 5 / 5A 6 / 6A C4 / C4A C5 / C5A C6 / C6A C7 / C7A Anti-reflective coating s s s s s s Anti-fog precursor coating YesCompoundVIII YesCompoundIII YesCompoundIX YesCompoundX YesCompoundIX YesCompoundX Deposition method for theanti-fog precursor coating Evaporation Evaporation Evaporation Evaporation Evaporation Evaporation Drying for 1 hour at 60 ° C of the precursor anti-fog coating No No No No Yes Yes Anti-dirt coating No No No No No No Angle of static contact with water (°) beforeDefog it application 41(ex. 5) 36(ex. 6) 34(ex. C4) 31(ex. C5) 32(ex. C6) 29(ex. C7) Petition 870190016216, of 02/18/2019, p. 55/116 46/49 Anti-fog index after 0smear operation * THE THE THE THE THE THE Anti-fog index after 2smear operations * THE THE THE Ç Ç B Anti-fog index after 5smear operations * THE THE B Ç Ç B or C Anti-fog index after 10smear operations * A or C THE Ç Ç Ç Ç Anti-fog index after 20smear operations * Ç B Ç Ç Ç Ç [00215] * From the glasses comprising the anti-fog coating (after application of the surfactant). The number of drying operations indicated is an accumulated number. DURABILITY OF THE ANTI-SMOOTH EFFECT AFTER A MECHANICAL STRESS (AFTER APPLICATION OF THE DEFOG IT SOLUTION) [00216] This test makes it possible to evaluate the smear resistance of the temporary anti-fog solution on the lens surface. It is performed on two samples of each lens. Petition 870190016216, of 02/18/2019, p. 56/116 47/49 [00217] The deposition of the temporary anti-fog solution has been carried out in such a way that, at the beginning, all lenses can be considered as anti-fog glasses at the end of the hot steam test described here above. [00218] After each hot steam test, the lenses must be dried at room temperature, so that the water film due to fog disappears. In fact, if the glasses are rubbed while the water film is still present, the anti-fog solution is partially removed. [00219] The lenses are thus rubbed manually with a Cémoi® smear fabric (2 drying operations) and for the second time subjected to the hot steam test, then rubbed as previously described. A smear operation corresponds to two very marked rotations of a Cémoi® smear tissue on the lens surface. [00220] The lenses are then manually rubbed with a Cémoi® smear tissue (3 additional smear operations) and for the third time subjected to the hot steam test, allowing to allocate an anti-fog index after 5 smear operations, then rubbed as previously described. This cycle is repeated in order to allow an anti-fog index to be allocated after 10 and 20 accumulated smear operations, by making a series of 5, then a series of 10 additional smear operations, with a drying step between them. [00221] The anti-fog indexes (A, B, C or D) correspond to the fog level at the end of each hot steam test, after implementing the corresponding number of smear operations (accumulated number): A: Homogeneous water film (accurate 10/10) B: Visual distortion considered acceptable by a user C: Visual distortion considered as not acceptable by the user (heterogeneous water film) D: Totally diffuse white mist, fine drops of water. [00222] The lenses are considered to have successfully passed the durability test if they obtained an A or B result. RESULTS Petition 870190016216, of 02/18/2019, p. 57/116 48/49 [00223] It is clearly apparent that the organosilane compounds of the invention, corresponding to formulas III and VIII, allow the formation of anti-fog coatings that are more efficient than the comparative compounds of formulas IX and X used in the prior art, which have a very long polyoxyalkylene chain. This result is surprising, given that compounds IX and X allow to form more hydrophilic coatings than compounds III and VIII, and that better anti-fog properties are generally expected when increasing the hydrophilic character of a coating. Compound III is, in addition, appreciably more efficient than compound VIII. [00224] Furthermore, the heat pretreatment at 60 ° C for one hour, as carried out in comparative examples C6 and C7, in accordance with the teachings of application JP 2005-281143, did not have much influence on the performance of the anti-coating - fog. 6. EXAMPLE 7 [00225] Glasses made of an ORMA® material and comprising on its concave and convex faces the same functional coatings as those of examples 5-6, that is, to say that an impact resistant initiator based on polyurethane, a coating abrasion resistant and the anti-reflective coating Y (ZrO2 / SiO2 / ZrO2 / ITO / SiO2) is coated by vacuum evaporation on both sides of it, with a 2 nm thick layer of anti-dust coating on the Optool DSX ® material marketed by company Daikin Industries. [00226] A mask, made by laser cutting a plastic film to form a pattern here is then arranged on its convex face. The convex face, partially protected by the mask, is thus subjected to an argon ion bombardment using an ionic weapon, which causes the anti-dirt coating to be removed in the area that was not protected by the mask, in the shape of the pattern, and in this area the outer layer of the anti-reflective coating Y - which is a layer based on silica - to be exposed. [00227] Thus, in the exposed area, the vapor phase deposition of the anti-fog precursor coating is carried out in the same way as for examples 5-6, Petition 870190016216, of 02/18/2019, p. 58/116 49/49 by the use of formula III organosilane, and by fixing the mask to the surface of the lenses for deposition, in order to form a 2-3 nm thick layer graft with a precursor coating of the anti-fog coating. [00228] To demonstrate the properties of the glass, a few drops of the Clarity® Defog It solution are applied to its convex surface, then this surface is rubbed with a Cémoi® smear fabric. After a number of smear operations, the surfactant solution has been completely removed from the surface of the glass coated with the anti-dirt coating, while it is still present in the area corresponding to the pattern. [00229] This can be visually verified by subjecting the then prepared pair of glasses to the breath test, the refrigerator test or the hot steam test, mist appearing on the entire surface of the glasses, except in the area corresponding to the model, which is coated with an anti-fog coating according to the invention.
权利要求:
Claims (17) [1] 1. Lens for glasses comprising a substrate coated with a coating comprising silanol groups on its surface and, directly contacting this coating, a precursor coating of an anti-fog coating, in which the precursor coating of the anti-fog coating is: - obtained by grafting at least one organosilane compound having: - a polyoxyalkylene group comprising less than 80 carbon atoms, and - at least one silicon atom having at least one hydrolyzable group, characterized by the fact that - the precursor coating of the anti-fog coating has a thickness less than or equal to 5 nm, - the precursor coating of the anti-fog coating has a static contact angle with water of more than 10 ° and less than 50 °. [2] 2. Eyeglass lens according to claim 1, characterized in that the precursor coating of the anti-fog coating is coated with a film of a liquid solution comprising at least one surfactant and / or hydrophilic compound with no active properties of the surface. [3] Lens according to claim 2, characterized in that the precursor coating of the anti-fog coating is coated with a film of a liquid solution comprising at least one surfactant comprising poly (oxyalkylene) groups. [4] 4. Lens for glasses, according to claim 2, characterized by the fact that it has a static contact angle with water less than or equal to 10 o . [5] 5. Eyeglass lens according to any one of claims 1 to 4, characterized by the fact that the coating comprising silanol groups on its surface is an anti-reflective coating or a silica-based layer deposited in an abrasion resistant coating. Petition 870190109203, of 10/28/2019, p. 6/11 2/4 [6] 6. Eyeglass lens according to any one of claims 1 to 5, characterized in that the organosilane compound is a compound of the formula: R 1 YmSi (X) 3-m (I) in which Y groups, being the same or different, are monovalent organic groups linked to silicon through a carbon atom, groups X, being the same or different, are group hydrolysable, R 1 is a group comprising a polyoxyalkylene function, m is an integer equal to 0, 1 or 2. [7] 7. Eyeglass lens according to claim 6, characterized by the fact that the organosilane compound is a compound of the formula: Ym (X) 3-mSi (CH2) n '- (L') m '- (OR) nO- (L) mR' (II) where R 'is a hydrogen atom, an acyl group or an alkyl group , linear or branched, optionally substituted by one or more functional groups, and optionally comprising one or more double bonds, (OR) n is a polyoxyalkylene group such that R is a linear or branched alkylene group, L 'and L ”are divalent groups , X, Y and m are as defined in claim 6, n 'is an integer ranging from 1 to 10, n is an integer ranging from 2 to 30, m' is 0 or 1 and ”is 0 or 1. [8] 8. Eyeglass lens according to claim 7, characterized by the fact that R 'is an alkyl group. [9] 9. Eyeglass lens according to claim 7 or 8, characterized by the fact that m '' = 0. [10] 10. Eyeglass lens according to any one of claims 7 to 9, characterized in that the organosilane compound is a compound of formula (II) where n = 5 to 30. [11] 11. Eyeglass lens according to any one of claims 1 to 10, characterized in that the organosilane compound is a trialkoxysilane [alkoxy (polyalkylenoxy) alkyl]. Petition 870190109203, of 10/28/2019, p. 7/11 3/4 [12] 12. Eyeglass lens according to any one of claims 1 to 11, characterized in that the organosilane compound has no fluorine atom. [13] 13. Eyeglass lens according to any one of claims 1 to 12, characterized in that the polyoxyalkylene group of the organosilane compound comprises less than 60 carbon atoms. [14] 14. Method for preparing an eyeglass lens as defined in any of claims 1 to 12, characterized in that it comprises the steps of: - providing a substrate coated with a coating comprising silanol groups on its surface, - depositing in said coating at least one organosilane compound having a polyoxyalkylene group comprising less than 80 carbon atoms and at least one silicon atom having at least one hydrolyzable group, in order to obtain a layer of grafted organosilane compound having a smaller thickness than or equal to 5 nm, the surface of which has a static contact angle with water of more than 10 o and less than 50 o . [15] 15. Method according to claim 14, characterized in that the layer of grafted organosilane compound having a thickness less than or equal to 5 nm is obtained by removing the deposited, but not grafted, organosilane compound in excess on the coating surface comprising silanol groups. [16] 16. Method according to claim 14 or 15, characterized in that said organosilane compound is deposited by vacuum evaporation in said coating comprising silanol groups on the surface thereof. [17] 17. Optical article comprising a substrate coated with a coating comprising silanol groups on its surface, a portion of the surface of said coating comprising silanol groups on its surface being in direct contact with, and adhering to, a hydrophobic coating and / or Petition 870190109203, of 10/28/2019, p. 11/11 4/4 oleophobic, characterized by the fact that another part of the surface of said coating comprising silanol groups on its surface is in direct contact with a precursor coating of an anti-fog coating as defined in any of claims 1 to 13.
类似技术:
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公开号 | 公开日 FR2954833B1|2013-03-22| EA201200976A1|2012-12-28| EA022678B1|2016-02-29| JP5965321B2|2016-08-03| WO2011080472A2|2011-07-07| EP2519474B1|2015-04-01| JP2013516638A|2013-05-13| EP2519474A2|2012-11-07| BR112012016406A2|2018-05-15| IN2012DN05119A|2015-10-23| PT2519474E|2015-07-21| ES2539711T3|2015-07-03| FR2954832A1|2011-07-01| AU2010338060A1|2012-07-12| KR20120107084A|2012-09-28| AU2010338060B2|2015-01-22| US8709588B2|2014-04-29| CN102686527A|2012-09-19| CA2785908A1|2011-07-07| KR101764280B1|2017-08-03| CN102686527B|2015-08-05| WO2011080472A3|2011-08-25| PL2519474T3|2015-08-31| FR2954833A1|2011-07-01| CA2785908C|2018-09-11| US20120019767A1|2012-01-26|
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法律状态:
2018-06-12| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]| 2018-06-19| B25A| Requested transfer of rights approved|Owner name: SATISLOH AG (CH) | 2018-12-18| B06T| Formal requirements before examination [chapter 6.20 patent gazette]| 2019-07-30| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]| 2020-02-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]| 2020-04-14| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |
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申请号 | 申请日 | 专利标题 FR0959685A|FR2954832A1|2009-12-31|2009-12-31|OPTICAL ARTICLE COMPRISING A TEMPORARY ANTIBUID COATING WITH IMPROVED DURABILITY| FR0959685|2009-12-31| FR1053269A|FR2954833B1|2009-12-31|2010-04-28|OPTICAL ARTICLE COMPRISING A TEMPORARY ANTIBUID COATING WITH IMPROVED DURABILITY| PCT/FR2010/052895|WO2011080472A2|2009-12-31|2010-12-22|Optical article comprising a temporary anti-fogging coating with improved durability| 相关专利
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