optical article comprising a temporary anti-fog coating based on surfactant with improved durability

专利摘要:
OPTICAL ARTICLE THAT UNDERSTANDS A TEMPORARY ANTI-PUMPING COATING BASED ON SURFACE WITH IMPROVED DURABILITY. It is an optical article that comprises a substrate coated with a coating that preferably comprises silanol groups on its surface and, in direct contact with that coating, a precursor coating of anti-fog coating, the said precursor coating having preferably an angle of static contact with water of more than 10 ° and less than 50 ° and is obtained by grafting at least one organosilane compound that has a polyoxyalkylene group and at least one silicon atom that bears at least one hydrolyzable group and is additionally coated with a film obtained by applying a composition containing at least one surfactant of formula F (CF2) y- (CH2-CH2O) x + 1H (VIII), where x is an integer that is in a range of 1 to 14, y is an integer less than or equal to 10, compounds of formula (VIII) in which y = 6 represents at least 90% by weight by weight, in relation to the weight of the compounds (VIII) present in the composition, of so the form an anti-fog coating, which preferably has a smaller static contact angle with water (...).
公开号:BR112014001458B1
申请号:R112014001458-2
申请日:2012-06-28
公开日:2021-03-09
发明作者:Mamonjy Cadet；Annette Cretier；Charlotte SAINT-LU
申请人:Satisloh Ag；
IPC主号:

专利说明:

[0001] The present invention relates to an optical article, preferably an eyeglass lens, which comprises a precursor anti-fog coating, characterized by the fact that the precursor anti-fog coating is coated with a composition, preferably a liquid solution. , which contains at least one surfactant corresponding to the formula F (CF2) y- (CH2-CH2O) x + 1H (VIII), where y is an integer less than or equal to 10 and compounds of formula (VIII), in whereas y = 6, are responsible for at least 90%, preferably at least 95% and more preferably 100% by weight of compounds of formula (VIII) present in the composition; x is an integer in the range 1 to 14.
[0002] The present invention also relates to a method for imparting anti-fog properties to an optical article, preferably a spectacle lens, which comprises a step for depositing the composition on the surface of the article, preferably the liquid solution, as above.
[0003] The present invention also relates to anti-fog fabrics impregnated with said composition.
[0004] Very numerous supports, such as plastic materials and glass, suffer from a disadvantage when they are covered with fog when their surface temperature decreases below the dew point of the ambient air. This is spatially the case with glass or organic glass that is used to perform vitrification for transport vehicles or buildings, lenses, especially for glasses, mirrors and so on. The haze that develops on these surfaces leads to a decrease in transparency, due to the diffusion of light through the water droplets, which can cause substantial discomfort.
[0005] To prevent any formation of fogging in very humid environments, that is, the condensation of very small water droplets on a support, it has been suggested the application of hydrophilic coatings on the external surface of such support, with a static contact angle low with water, preferably less than 50 °, more preferably less than 25 °. Such permanent anti-fog coatings act as sponges in relation to fogging and allow water droplets to adhere to the surface of the substrate by forming a very thin film that creates the impression of transparency. These coatings are generally made from highly hydrophilic species such as sulfonates or polyurethanes.
[0006] The commercially available products comprise hydrophilic layers of several micrometers in thickness.
[0007] As a rule, when the thickness of the coatings is high (several microns), these coatings, as a result of water absorption, expand, soften and become mechanically less resistant.
[0008] As used herein, a permanent anti-fog coating is intended to mean a coating whose hydrophilic properties result from the hydrophilic compounds permanently bonded to another coating or support. EP 1324078 describes a lens coated with an abrasion resistant coating and a multi-layered anti-reflective coating comprising layers with alternating high and low refractive indexes, among which the outer layer is a low refractive index layer (1, 42 to 1.48) from 5 to 100 nm thick that forms an anti-fog coating consisting of a hybrid layer with a static contact angle with water less than 10 °, obtained by depositing simultaneously an organic compound and silica or silica and alumina, that is, through the coevaporation of these various components. The anti-fog coating preferably comprises from 0.02 to 70% by weight of the organic compound in relation to the total weight of the coating and typically from 6 to 15% by weight, according to the examples.
[0009] Said organic compound comprises a hydrophilic group and a reactive group, for example, a trialcoxysilyl group which has from 3 to 15 carbon atoms and preferably has a molecular weight in the range of 150 to 1,500 g / mol. Some preferred compounds have a polyether backbone, 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.
[0010] The anti-fog coating, then, appears as a layer based on silica (or a layer based on silica + alumina) that incorporates a hydrophilic organic compound. However, its anti-fog character does not change over time and a deterioration in stages of the anti-fog properties can be observed. When it becomes too low, it can be restored through a "wash treatment" of the anti-fog film, particularly a plasma-mediated treatment.
[0011] In practice, the EP 1324078 coevaporation method is very complicated to deploy. It would be preferable to have a method for producing an anti-fog coating without performing any coevaporation process.
[0012] The patents in US 6,251,523 and US 6,379,776 describe an anti-reflective and anti-fog glass for cars or lenses comprising a glass substrate provided with a silica-based anti-reflective coating with a thickness of 110 to 250 nm with a roughness surface Ra of about 5 to 10 nm, in turn provided with a permanent anti-fog coating with 8 nm of thickness obtained through a deposition of liquid or vapor 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 static contact angle with water of 3 °.
[0013] Another solution to combine anti-reflective and anti-fog properties is to use a thin, low porous refractive index layer, partially made of surfactants, which allows the layer to acquire anti-fog properties. This layer is usually deposited on a hydrophilic surface.
[0014] Thus, US patent 5,997,621 describes a porous anti-fog and anti-reflective coating based on metal oxides (silica microspheres) and relatively water-soluble anionic surfactants, which generally have an ionic hydrophilic carboxylic acid head, sulfonate or phosphate type and a fluorinated chain. In order to be immobilized on a substrate, surfactants can preferably be covalently bonded to metal oxides. The application in WO 97/43668 describes a similar construction.
[0015] The application in EP 0871046 describes an anti-reflective and anti-fogging system comprising a porous layer based on inorganic oxide deposited in a water-absorbent layer of a thickness of a few micrometers, obtained by polycondensation of an inorganic alkoxide hydrolyzate in the presence of a polyacrylic acid compound. The porous layer, which acts as the anti-reflective barrier, allows water to access the absorbent layer.
[0016] The anti-fog properties can also be obtained by applying temporary commercially available solutions such as sprinkles or wipes, on spectacle lenses that comprise the outer layer as an anti-dust coating (hydrophobic and oleophobic), normally considered essential when ophthalmic lenses they are provided with an anti-reflective coating. They make it possible to obtain the anti-fog property in a short period of time. The aspect of ease of removing dirt that is given to the anti-dust coating is preserved, but after some cleaning operations, the anti-fogging property is significantly changed. In fact, the temporary solutions comprise materials that are hydrophilic in nature with poor interactions with the hydrophilic surface of the anti-dust coating, so that after some cleaning operations, these hydrophilic materials are removed.
[0017] A more interesting solution is to produce 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.
[0018] EP 1275624 describes a lens coated with a hydrophilic, inorganic, hard layer based on metal oxides and silicon oxide. Its hydrophilic nature and the presence of concave portions of nano size on the surface of the same allows the impregnation of a surfactant and the retention of it adsorbed for a long period of time, thus maintaining an anti-fogging effect for several days. However, an anti-fog effect can also be observed in the absence of any surfactant.
[0019] The orders in JP 2004-317539 and JP 2005-281143 describe a lens coated with an anti-reflective coating with multiple layers and / or with an abrasion resistant coating and with a precursor coating of anti-fog coating, which has a contact angle static with water from 50 ° to 90 °. The anti-fog coating as such, which is a temporary coating, is obtained after the application of a surfactant on the surface of the precursor coating.
[0020] The precursor coating of anti-fog coating is obtained from a composition comprising an organic compound comprising a hydrophilic group of a polyoxyethylene nature, a reactive group that can react with the outer layer of the anti-reflective coating, especially a base layer of silica, such as alkoxysilane Si (OR) n, silanol SiOH or isocyanate groups and optionally a hydrophobic fluorinated group and the composition is chosen so that the angle of static contact with the water of the precursor coating of anti-fog coating varies from 50 ° to 90 °. The organic compounds used in the anti-fog coating precursor preferably have a molecular weight in the range of 700 to 5,000 or 430 to 3,700 g / mol. The CH3O (CH2CH2O) 22CONH (CH2) 3Si (OCH3) 3 or C8F17O (CH2CH2O) 2CONH (CH2) 3Si (OCH3) 3 compounds are mentioned as examples of such compounds. The precursor coating is described as being 0.5 to 20 nm thick. The relatively high contact angle of the precursor coating is expected due to the fact that it allows, according to these requests, the easy removal of dirt resulting from the removal of water droplets.
[0021] The patent application in WO 2011/080472 describes a lens for glasses which comprises a substrate provided with a coating comprising silanol groups on the surface of the same and in direct contact with that coating, a precursor coating of anti-fog coating, in which the precursor coating of anti-fog coating:
[0022] - is obtained by grafting at least one organosilane compound that has:
[0023] - a polyoxyalkylene group comprising less than 80 carbon atoms and
[0024] - at least one silicon atom that carries at least one hydrolyzable group,
[0025] - has a thickness less than or equal to 5 nm,
[0026] - has a static contact angle with water greater than 10 ° and less than 50 °.
[0027] The solution that is preferably deposited to provide that surface with anti-fog properties is the commercially available solution Defog it ™.
[0028] The anti-fog properties, especially the durability of the anti-fog effect associated with the lens precursor coating described in the patent application in WO 2011/080472, are very satisfactory.
[0029] However, it is desirable to improve the anti-fog performance of spectacle lenses, which are described in the patent application in WO 2011/080472. Particularly, layers with more effective anti-fog properties are seen afterwards, which could last longer over time and / or under mechanical stresses, while preserving an acceptable dirt removal facility.
[0030] Anti-fog coatings that also have good mechanical properties (abrasion and scratch resistance) are also seen below.
[0031] The present invention aims to prepare such temporary anti-fog coatings, which significantly improve the durability of the anti-fog property over time and / or under mechanical stresses.
[0032] It is an additional object of the present invention to provide an anti-fog coating that could be immediately operational, that is, a coating that, when a transparent lens substrate coated with such a coating is placed under conditions that generate fog on said substrate which is devoid of of the said coating, makes it possible to obtain (in less than a second) a vision> 6/10 (visual acuity) and preferably 10/10, without the formation of haze for an observer looking through a lens coated with according to the Snellen E visual acuity scale (ARMAIGNAC (Tridents) scale (Snellen E) that reads at 5 meters, ref. T6 available from FAX INTERNATIONAL), located at a distance of 5 meters.
[0033] It is an additional object of the present invention to provide an optical article which has both anti-reflective and anti-fog properties.
[0034] These objectives can be achieved, according to the invention, thanks to the application in the optical article of a composition, preferably a liquid solution, containing at least one surfactant that corresponds to the formula F (CF2) y- (CH2-CH2O ) x + 1H (VIII), where y is an integer less than or equal to 10, compounds of formula (VIII) where y = 6, are responsible for at least 90% by weight, preferably at least 95%, more preferably 100% by weight of compounds of formula (VIII) present in the composition, preferably a liquid solution ex is an integer in the range 1 to 14.
[0035] In another modality, x in formula (VIII) is an integer from 2 to 14. The description is detailed below with reference to the modality in which x in formula (VIII) is an integer from 1 to 14, but the The following description and all the features described and preferred also apply to the modality in which x, in formula (VIII), is an integer from 2 to 14.
[0036] In the remainder of the specification, the modalities for a liquid surfactant solution will be described in more detail.
[0037] Preferably, the compounds of formula (VIII), where y is greater than 6, are present in an amount less than 5% by weight, preferably less than 2% by weight and more preferably 0%, in relation to weight of compounds (VIII) present in the composition. Preferably, the liquid solution does not comprise surfactants other than those of formula VIII.
[0038] In another embodiment, the surfactant-containing composition does not comprise any compounds of formula (VIII), where y = 10.
[0039] Preferably, the compounds of formula (VIII), where x is in the range 1 to 4, are present in an amount of at least 50% by weight, preferably at least 60% by weight, in relation to the weight of compounds (VIII) present in the composition.
[0040] Preferably, the compounds of formula (VIII), where x is in the range 1 to 5, are present in an amount of at least 70% by weight, preferably at least 80% by weight, in relation to the weight of compounds (VIII) present in the composition.
[0041] As is well known to the person skilled in the art, the weights corresponding to each of the fractions defined by the pairs (x, y) can be determined using HPLC, coupled to a mass spectrometry.
[0042] Thus, the present invention relates to an optical article, preferably a lens for glasses, which comprises a substrate with a first coating and, in direct contact with that first coating, a precursor coating of anti-fog coating, characterized by fact that the precursor coating of anti-fog coating:
[0043] - is obtained by grafting at least one organosilane compound that has:
[0044] - a polyoxyalkylene group and
[0045] - at least one silicon atom that carries at least one hydrolyzable group,
[0046] - preferably has a thickness less than or equal to 5 nm,
[0047] - preferably has a static contact angle with water greater than 10 ° and less than 50 °.
[0048] and is also coated with a film obtained by applying the composition, preferably the liquid surfactant solution as previously defined and forming an anti-fog coating, which preferably has a static contact angle with water less than or equal to 10 ° , more preferably less than or equal to 5 °.
[0049] In the present application, a coating that is "on" a 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) does not is 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) it does not necessarily cover the entire substrate / coating. When “a layer 1 is arranged under a layer 2”, it means that layer 2 is more distant from the substrate than layer 1.
[0050] As used herein, an "anti-fog coating" means a coating that, when a transparent lens substrate coated with such a coating is placed under conditions that cause fogging on said substrate that is devoid of said coating, makes it possible to obtain immediate visual acuity> 6/10 for an observer looking through a lens coated on a visual acuity scale located at a distance of 5 meters. Several tests to assess the anti-fog properties of a coating are described in the experimental section. Under fogging conditions, anti-fog coatings may or may not be present on its surface (ideally, none, visual distortion or visual distortion, but visual acuity> 6/10 under the measurement conditions mentioned above) or some may be present blurring on its surface, but still allow, despite the visual disturbance resulting from the blurring, a visual acuity> 6/10 under the measurement conditions mentioned above. A non-fogging coating does not allow visual acuity> 6/10 while it is exposed to conditions that generate fogging and generally presents a condensation mist under the measurement conditions mentioned above.
[0051] As used herein, an "anti-fog optical article" is intended to mean an optical article with a "anti-fog coating" as defined above.
Thus, the anti-fog coating precursor 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, which can be observed, for example. example, through a breath test described in the experimental section. In fact, this anti-fog coating precursor does not allow a visual acuity> 6/10 to be obtained under the measurement conditions mentioned above.
[0053] As used herein, a temporary anti-fog coating is intended to mean an anti-fog coating obtained after application of the liquid solution containing the formula (VIII) surfactant on the surface of the precursor coating of said anti-fog coating. The durability of a temporary anti-fog coating is generally limited by the cleaning operations carried out on its surface, in which the surfactant molecules are not permanently attached to the surface of the coating, but only adsorbed for a more or less durable period of time.
[0054] The optical article prepared according to the invention comprises a substrate, preferably transparent, which has front and rear main surfaces, in which at least one of said main surfaces is provided with a coating preferably comprising silanol groups on the surface thereof , preferably on both main surfaces. As used in this document, the back face (usually concave) of the substrate is intended to mean the face that, when using the article, is the closest to the user's eye. Conversely, the front face (usually convex) of the substrate is the face that, when using the article, is the furthest from the user's eye.
[0055] Although the article according to the invention can be any optical article that may present a problem of fog formation, such as a screen, a glazing of the automotive or construction industry, or a mirror, it is preferably a try optics, more preferably an ophthalmic lens, for glasses, or a rough block for optical or ophthalmic lenses.
[0056] This excludes articles, such as intraocular lenses, which are in contact with living tissues or contact lenses, which do not intrinsically present the problem of fogging, as opposed to spectacle lenses.
[0057] According to the invention, the coating comprising silanol groups on its surface can be formed on at least one of the main surfaces of a bare substrate, that is, an uncoated substrate, or on at least one of the main surfaces of a substrate that has already been coated with one or more functional coatings.
[0058] The substrate for the optical article according to the invention can be a mineral or an organic glass, for example, of a thermostable or thermoplastic plastic material.
[0059] Especially preferred classes of substrates include poly (thiourethanes), polysulfites and resins resulting from the polymerization or (co) polymerization of alkylene glycol bis allyl carbonates. These are sold, for example, under the trade name CR-39® by the company PPG Industries (ORS® lenses, from ESSILOR).
[0060] In some applications, it is preferable that the main surface of the substrate is coated with one or more functional coatings before deposition of the coating comprising silanol groups on its surface. These functional coatings traditionally used in optics can be, without limitation, an impact resistant initiator layer, an abrasion resistant and / or scratch resistant coating, a polarized coating, a photochromic coating or a colored coating, particularly an I 'layer. . impact resistant primer coated with an abrasion resistant and / or scratch resistant layer.
[0061] The coating comprising silanol groups on its surface is preferably deposited in an abrasion resistant and / or scratch resistant coating. The abrasion resistant coating and / or the scratch resistant coating can be any traditionally used as an abrasion resistant coating and / or the scratch resistant coating in the field of ophthalmic lenses.
[0062] Abrasion resistant and / or scratch resistant coatings are preferably hard coatings based on poly (meth) acrylates or silanes which generally comprise one or more mineral fillers which are intended to improve hardness and / or refractive index of the coating once cured. As used herein, a (meth) acrylate is an acrylate or a methacrylate.
[0063] The abrasion-resistant coating and / or the scratch-resistant hard coatings are preferably made of compositions comprising at least one alkoxysilane and / or a hydrolyzate thereof, obtained, for example, by hydrolysis with a hydrochloric acid solution and optionally condensation and / or curing catalysts and / or surfactants.
The recommended coatings of the present invention include coatings based on epoxysilane hydrolysates, such as those described in patents in EP 0614957, US 4,211,823 and US 5,015,523.
[0065] The thickness of the abrasion resistant coating and / or scratch resistant coating generally varies from 2 to 10 μm, preferably from 3 to 5 μm.
[0066] Before deposition of the abrasion resistant coating and / or the scratch resistant coating, it is possible to apply an initiator coating on the surface to improve the impact resistance and / or the adhesion of the subsequent layers in the final product.
[0067] This coating can be any impact resistant primer layer traditionally used for articles in a transparent polymeric material, such as ophthalmic lenses. ■
[0068] Preferred initiator compositions can be chosen from those described in the document in WO 2011/080472, which is incorporated herein by reference.
[0069] Preferred initiator compositions are compositions based on polyurethanes and compositions based on latex, particularly latex of the polyurethane type and poly (meth) acrylic latex and combinations thereof. The primer layers in general have thicknesses, after curing, in the range of 0.2 to 2.5 μm, preferably in the range of 0.5 to 1.5 μm.
[0070] The coating comprising silanol groups on its surface will be described below. As used herein, a coating comprising silanol groups on its surface is intended to mean a coating naturally comprising silanol groups on its surface or a coating whose silanol groups were created after being subjected to a surface activation treatment. This coating is therefore siloxane or silica based, for example, without limitation, a silica based layer, a sun gel coating, based on organosilane species such as alkoxysilanes or a silica colloid based coating. . The first coating, which preferably comprises silanol groups on its surface, can be especially an abrasion-resistant and / or scratch-resistant coating or, according to the preferred embodiment, an anti-reflective coating with one layer or an anti-reflective coating with multiple layers whose outer layer 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.
[0071] The surface activation treatment that generates the silanol groups or at least increases their proportion on the surface of a coating is generally carried out under vacuum. The same 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 corona discharge treatment, a ion fragmentation treatment, an ultraviolet treatment or a vacuum-mediated plasma treatment, usually using an argon or oxygen 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.
[0072] As used in this document, energetic species (and / or reactive species) are intended to mean especially ionic species with an energy in the range of 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.
[0073] The activation treatment can also be an acidic or basic chemical surface treatment, preferably a wet treatment or a treatment with the use of a solvent or a combination of solvents.
[0074] The coating comprising silanol groups on its surface is preferably a layer with a low refractive index based on silica (which comprises silica), more preferably it consists of a layer based on silica (SiO2), generally obtained through vapor phase deposition.
[0075] Said layer based on SiO2 may comprise, in addition to silica, one or more other materials traditionally used to produce thin layers, for example, one or more materials selected from dielectric materials described previously in this specification. This SiO2-based layer is preferably free of AI2O3.
[0076] 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 groups 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 noted, in a form of maximum preference, it comprises 100% by weight of silica.
The coating comprising silanol groups on its surface can also be a silane-based sol-gel coating, such as alkoxysilanes, for example, tetraethoxysilane or organosilanes such as y-glycidoxypropyl trimethoxysilane. Such coating is obtained by wet deposition, using a liquid composition comprising a hydrolyzate of silanes and optionally colloidal materials with a high refractive index (> 1.55, preferably> 1.60, more preferably> a 1, 70) or low (<1.55). Such a coating whose layers comprise an organic / inorganic hybrid matrix based on silanes in which colloidal materials are dispersed to adjust the refractive index of each layer is described, for example, in the patent in FR 2858420.
[0079] In one embodiment of the invention, the coating comprising silanol groups on its surface is a silica-based layer deposited in an abrasion resistant coating, preferably directly deposited in that abrasion resistant coating.
[0080] Said silica-based layer (which comprises 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 in the range of 5 to 20 nm and even more preferably from 10 to 20 nm.
[0081] Preferably, the deposition of said layer based on silica is carried out by regulating the pressure, which means by adding gas to the deposition chamber, in which the gas is in a non-ionic form, preferably by adding oxygen, at a pressure in the range typically 0.01 to 0.05 Pa (5-10-5 to 510-4 mbar).
[0082] 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 groups on the surface thereof within the meaning of the invention. This antireflective coating can be any antireflective coating traditionally used in the optical field, particularly ophthalmic optics, as long as it comprises silanol groups on its surface.
[0083] An anti-reflective coating is defined as a coating, deposited on the surface of an optical article, which improves the anti-reflective properties of the final optical article. This makes it possible to reduce the reflection of light at the interface between article and air over a relatively large portion of the visible spectrum.
[0084] As is also well known, anti-reflective coatings traditionally comprise a monolayer or multiple layer cell composed of dielectric materials. These are preferably multi-layer coatings, which comprise layers with a high refractive index (Hl) and layers with a low refractive index (LI).
[0085] In the present application, a layer of the 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 layer with a low refractive index 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 ° C at a wavelength of 550 nm.
[0086] The layers H1 and LI are traditional layers well known in the art, generally comprising one or more metal oxides, which can be chosen, without limitation, from the materials disclosed in the document in WO 2011/080472.
[0087] When a LI layer comprising a mixture of SiO2 and AI2O3 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 AI2O3 in relation to the weight total SiO2 + AI2O3 in that layer.
[0088] Typically, the H1 layers have a physical thickness in the range of 10 to 120 nm and the LI layers have a physical thickness in the range of 10 to 100 nm.
[0089] Preferably, the total antireflection thickness is less than 1 micron, more preferably less than or equal to 800 nm and even more preferably less than or equal to 500 nm. The total antireflection thickness is generally greater than 100 nm, preferably greater than 150 nm.
[0090] 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 (Hl). 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.
[0091] The layers Hl and LI do not need to be alternated with each other in the anti-reflective coating, although they can also be, according to an embodiment of the invention. Two layers H1 (or more) can be deposited with each other, just as two layers LI (or more) can be deposited with each other.
[0092] The various layers of the anti-reflective coating can be deposited according to any of the methods disclosed in the document in WO 2011/080472, which is incorporated by reference. A particularly recommended method is evaporation under vacuum.
[0093] When the coating comprising silanol groups on its surface is an anti-reflective coating, the luminous reflection factor of an article coated with such an anti-reflective coating, called Rv, is preferably less than 2.5% per face of the article. The means of achieving such Rv values are well known to the person skilled in the art.
[0094] In this application, the "light reflection factor" is as defined in the ISO 13666: 1998 standard and is measured according to the ISO 8980-4 standard, that is, it is the weighted average of the spectral reflectivity within the whole the visible spectrum wavelength range from 380 to 780 nm.
[0095] Before forming the anti-fog coating precursor in the coating comprising silanol groups on the surface of the coating, for example, an anti-reflective coating, it is usual to subject the surface of such coating to a physical or chemical activation treatment designed to reinforce adhesion precursor of anti-fog coating. These treatments can be selected from those previously described to activate the coating that comprises silanol groups on its surface.
[0096] According to the invention, the coating comprising silanol groups on its surface is in direct contact with the precursor coating of an anti-fog coating, which will be described below.
[0097] As used herein, "a precursor to an anti-fog coating" is intended to mean a coating which, if a liquid solution containing a surfactant is applied to the surface thereof to form a film, represents an anti-fog coating within the meaning of the invention. The precursor coating system + surfactant-based solution film represents the anti-fog coating as such.
[0098] The precursor coating of anti-fog coating is a coating that has a thickness preferably less than or equal to 5 nm, preferably of 4 nm or less, more preferably of 3 nm or less and even more preferably of 2 nm or less, which has preferably a static contact angle with water greater than 10 ° and less than 50 °, which is obtained through a permanent graft of at least one organosilane compound that has a polyoxyalkylene group and at least one silicon atom that bears at least a hydrolyzable group.
[0099] In one embodiment of the invention, the coating is deposited by applying a composition comprising a hydrolyzable organosilane compound that has a polyoxyalkylene group and at least one silicon atom that bears at least one hydrolyzable group.
[00100] It is recommended to avoid any condensation of the hydrolysed organosilane compounds so that they can keep as much as possible the free silanol functions to react in order to facilitate the grafting of these compounds on the surface of the optical article and to limit the formation of pre- siloxane polymers before grafting. It is for this reason that the thickness of the deposited organosilane compound is so thin.
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 the hydrolysis has been carried out (by adding a aqueous acid solution, typically based on HCI).
[00102] Most preferably, the composition is applied less than 10 minutes, even more preferably less than 5 minutes and preferably less than 1 minute after the hydrolysis has been carried out.
[00103] It is preferable to conduct hydrolysis without providing heat, that is, typically at a temperature of 20 to 25 ° C.
[00104] As a rule, the deposition of layers with a few nanometers in thickness requires the use of very diluted compositions, with a very low dry matter content, which reduces the condensation kinetics.
[00105] The organosilane compound used can, thanks to its reactive group containing silicon, establish a covalent bond with the silanol groups present on the surface of the coating where it is deposited.
The organosilane compound of the invention comprises a polyoxyalkylene chain functionalized at only one end or at both ends thereof, preferably at only one end, by a group comprising at least one silicon atom which bears at least one group hydrolyzable. This organosilane compound preferably comprises a silicon atom which bears at least two hydrolyzable groups, preferably three hydrolyzable groups. Preferably, it does not comprise any urethane group. It is preferably a compound of the formula:
[00107] R1YmSi (X) 3-m (I)
[00108] in which groups Y, which are the same or different, are monovalent organic groups linked to the silicon atom through a carbon atom, groups X, which are the same or different, are hydrolyzable groups, R1 is a group which comprises a polyoxyalkylene function, m is an integer equal to 0, 1 or 2. Preferably m = 0.
[00109] Groups X are preferably selected from alkoxy groups - O-R3, particularly C1-C4 alkoxy groups, acyloxy groups -OC (O) R4 in which R4 is an alkyl radical, preferably a C1-C6 alkyl radical, preferably a methyl or an 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 C1-C4, for example, an alkyl group, such as a methyl or ethyl group , 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.
[00111] In a preferred embodiment, the compound of formula I comprises a trialkoxysilyl group such as a triethoxysilyl or trimethoxysilyl group.
The polyoxyalkylene group of the organosilane compound (group R1) preferably comprises less than 80 carbon atoms, more preferably less than 60 carbon atoms and even more preferably less than 50 carbon atoms. Most preferably, the polyoxyalkylene group comprises less than 40 carbon atoms and more preferably less than 30 carbon atoms. The most preferred compounds have a polyoxyalkylene group that comprises from 5 to 20 carbon atoms. The group R1 preferably satisfies the same conditions.
[00113] The group R1 corresponds in general to the formula -L-R2. where L is a divalent group attached to the silicon atom of the compounds of formula I or II via a carbon atom and R2 is a group comprising a polyoxyalkylene group linked to the L group via an oxygen atom, where that atom oxygen is included in group R2. Non-limiting examples of groups L include optionally substituted linear or branched alkyl, cycloalkylene, arylene, carbonyl, starch groups, or combinations of these groups such as cycloalkylene alkylene, biscicloalkylene, biscicloalkylene alkylene, arylene alkylene, bisphenylene, bisenylene alkylene, alkylene starch, among which, for example, the CONH (CH2) 3 group or the -OCH2CH (OH) CH2- and -NHC (O) - groups. Preferred L groups are alkyl groups (preferably linear), which preferably have 10 carbon atoms or less, more preferably 5 carbon atoms or less, for example, ethylene and propylene groups.
The preferred R2 comprises a polyoxyethylene - (CH2CH2O) n- group, a polyoxypropylene group or combinations of these groups.
[00115] Preferred organosilanes of formula I are composed of the following formula II:
[00116] Ym (X) 3-mSi (CH2) n '- (L,) m' - (OR) n-O- (L ") m" -R '(II)
[00117] 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 further comprise one or more double bonds, R is a linear or branched alkyl group , preferably linear, for example, an ethylene or propylene group, L 'and L "are divalent groups, X, Y and m are as defined above, n' is an integer in the range 1 to 10, preferably 1 to 5 , n is an integer in the range of 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.
[00118] The groups L 'and L ", when present, can be selected from the divalent groups L previously described and preferably represent the group -OCH2CH (OH) CH2- or the group -NHC (O) -. In this case, the groups - OCH2CH (OH) CH2- or -NHC (O) - are attached to the adjacent groups (CH2) n '(with a group L') and R '(with a group L ") through their oxygen atom (for the -OCH2CH (OH) CH2- group) or through its nitrogen atom (for the -NHC (O) -) group ■
[00119] In one embodiment, m = 0 and the hydrolyzable groups X represent methoxy or ethoxy groups. n 'is preferably 3. In another embodiment, R' represents an alkyl group that has less than 5 carbon atoms, preferably a methyl group. R 'can also represent an aliphatic or aromatic acyl group, especially an acetyl group.
[00120] Finally, R 'may represent a trialcoxysilylalkylene group or a trialogenosylylalkylene group such as a - (CH2) n "Si (R5) 3 group where R5 is a hydrolyzable group such as the groups X defined above and n" is a number 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 that contain at least one hydrolyzable group.
[00121] In the preferred modalities, n is 3, or is in the range of 6 to 9, from 9 to 12, from 21 to 24, or if 25 to 30, preferably from 6 to 9.
[00122] Suitable compounds of formula II are mentioned, 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), marked by Gelest, Inc. or ABCR, the compound of formula CH3O- (CH2CH2O) 3- (CH2) 3Si (OCH3) 3 ( Villa), compounds of the formula CH3O- (CH2CH2O) n- (CH2) 3Si (OC2H5) 3 where n = 21 to 24, 2- [methoxy (poloethyleneoxy) propol] trichlorosilanes, 2- [acetoxy (polyethyleneoxy) propyl] trimethoxysilane of 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 [(3-methyldimethoxysilyl) propyl oxide] and compounds with two siloxane heads such as polyethylene-bis [(3-triethoxysilylpropoxy) -2-hydroxypropoxy] of formula (V), polyethylene-bis [(N, N'-triethoxysilylpropyl) -aminocarbonyl] oxide of formula (VI) with n = 10 to 15 and polyethylene-bis (triethoxysilylpropyl) oxide of formula (VII):


The preferred compounds of formula II are [alkoxy (polyalkylonoxy) alkyl] trialcoxysilanes or their trialogenated analogs (m = m '= m "= 0, R' = alkoxy).
[00124] Preferably, the organosilane compound of the invention has no fluorine atom. Typically, the weight ratio of fluorine to the precursor coating of anti-fog coating is less than 5%, preferably less than 1% by weight and more preferably 0%.
[00125] Preferably, the molecular weight of the organosilane compound according to the invention is in the range of 400 to 4,000 g / mol, preferably 400 to 1,500 g / mol, more preferably 400 to 1,200 g / mol, and even more preferably from 400 to 1,000 g / mol.
[00126] It is certainly possible to graft a mixture of compounds of formula I or II, for example, a mixture of compounds with different lengths of polyoxyalkylene RO chain.
[00127] In an embodiment of the invention, the anti-fog coating precursor comprises more than 80% by weight of an organosilane compound according to the invention, relative to the total weight of the anti-fog coating precursor, preferably more than 90%, more preferably more than 95% and most preferably more than 98%. In one embodiment, the anti-fog coating precursor consists of a layer of said organosilane compound.
Preferably, the anti-fog coating precursor of the invention comprises less than 5% by weight of a metal or metalloid oxide (for example, silica or alumina) relative to the total coating weight, more preferably it is free of any a. When the organosilane compound used to produce the anti-fog coating is deposited under vacuum, preferably no metal oxide is coevaporated, according to the coevaporation method of at least one organic compound and at least one inorganic compound described in the application in EP 1324078 .
[00129] Preferably, the precursor coating of anti-fog coating does not comprise any cross-linking agent, which means that it is preferably not formed of a composition comprising a cross-linking agent, for example, tetraethoxysilane.
[00130] The anti-fog coating precursor of the invention preferably has a static contact angle with water greater than 10 ° and less than 50 °, preferably less than or equal to 45 °, more preferably <40 °, even more preferably 2 30 ° and preferably <25 °. This contact angle is preferably in the range of 15 ° to 40 °, more preferably 20 ° to 30 °.
[00131] 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, preferably maximum in the gas phase, by vacuum evaporation.
[00132] 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 onto the surface of the coating that contains silanol group. The non-grafted molecules are thus removed. Such removal step should preferably be performed when the thickness of the anti-fog coating precursor initially deposited is greater than 5 nm.
[00133] 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, it is guaranteed that the deposited thickness do not exceed a few nanometers. Adjusting the deposition parameters to obtain such thicknesses is part of the ordinary competence of anyone skilled in the art.
[00134] However, it is preferable to form the precursor coating of anti-fog coating by depositing some excess organosilane compound on the surface of the coating comprising silanol groups and then removing the excess of that deposited compound, but not the grafted compound. In fact, the inventors have observed that when a layer of grafted organosilane compound is formed directly with a thickness less than or equal to 5 nm, which does not require any removal of 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 with a liquid solution comprising at least one surfactant, which could lead to a coating which does not have the desired anti-fog properties.
[00135] Surprisingly, this is not seen 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.
[00136] The removal of the organosilane compound deposited in excess can be carried out by washing (wet process) using, for example, a solution based on water and soap and / or by cleaning (dry process). Preferably, the removal step comprises a washing operation followed by a cleaning operation.
[00137] Preferably, the washing operation is performed by cleaning the article with soapy water (which includes a surfactant) with the use of a sponge. Therefore, a washing operation is performed with deionized water and, optionally, the lens is then subjected to a cleaning operation for typically less than 20 seconds, preferably 5 to 20 seconds, using a CEMOI ™ or Selvith handkerchief. ™ impregnated with alcohol, typically isopropyl alcohol. Another washing operation with deionized water can then be repeated, then a cleaning operation with a cleaning tissue. All of these steps can be performed manually or they can be partially or completely automated.
[00138] The step of removing excess organosilane compound leads to a layer of organosilane compound that is generally and preferably 5 nm thick or less. In that case, the organosilane compound deposited on the surface of the optical article forms a monomolecular or almost monomolecular layer.
[00139] The organosilane compound can be dissolved beforehand in a solvent before being evaporated, to better control the rate of evaporation and the rate of deposition. The thickness of the film can be controlled in this way thanks to dissolution and by adjusting the amount of solution to be evaporated.
[00140] When the graft is performed using a wet process, for example, by immersion or spin coating, it is generally not necessary to carry out a step to remove the excess deposited organosilane compound.
[00141] The precursor coating of anti-fog coating according to the invention has a low roughness. Typically, for an organosilane compound deposited by vapor phase, the average roughness Ra is less than 2 nm, typically about 1 nm. Ra is as defined in WO 2011/080472.
[00142] A temporary anti-fog coating according to the invention is obtained by depositing on the precursor anti-fog coating coating a film of a composition, preferably a liquid solution, comprising at least one surfactant of formula F (CF2) y- (CH2 - CH2O) x + 1 H (VIII), where y is an integer less than or equal to 10, compounds of formula (VIII), where y = 6, which are responsible for at least 90% by weight, preferably by minus 95%, more preferably 100% by weight of the compounds of formula (VIII) present in the composition, x is an integer in the range 1 to 14 and in another embodiment from 2 to 14.
[00143] This solution provides the optical article, preferably a lens for glasses, with a temporary anti-fog protection by creating on its surface a uniform layer that helps to disperse the water droplets on the surface of the optical article so that it does not form any fog. visible.
[00144] The application of surfactant solution can be carried out by any known method, especially by immersion or spin coating.
[00145] The surfactant solution is preferably applied by depositing a droplet of this solution on the surface of the anti-fog coating precursor and then spreading it so as to preferentially cover the entire precursor coating.
[00146] The applied surfactant solution is generally an aqueous solution which preferably comprises from 0.5 to 15%, more preferably from 2 to 8% by weight of surfactants having formula VIII, in relation to the weight of the liquid solution. The solution may also comprise alcohols, such as ethanol or isopropyl alcohol, in an amount generally less than 10% by weight.
[00147] The surfactant composition based on the compounds of formula (VIII) is surprisingly significantly more effective in providing long-lasting anti-fog properties, it can be used in reduced amounts compared to prior art surfactants, typically in amounts which are in a range of 2 to 5% by weight, more preferably 2 to 4% by weight, in relation to the weight of the composition.
[00148] In more preferred embodiments, a cloth or handkerchief is impregnated by the composition containing an inventive surfactant based on the compounds of formula (VIII) and the cloth is used directly to impart anti-fog properties to the optical article coated with the precursor coating by cleaning the same with said handkerchief.
[00149] There is, therefore, no need to previously deposit a droplet of the surfactant solution of the compounds of formula (VIII).
[00150] It has been revealed that a non-woven cloth whose structure comprises a hydrophilic polymer and a hydrophobic polymer impregnated by the surfactant compositions based on the compounds of formula (VIII) provides superior results in terms of transparency and durability.
[00151] An example of such a cloth is the 'wetlaid' cloth manufactured with the Ahlstrom company.
[00152] In fact, without limitation to a theory, the inventors believe that the hydrophilic polymer on one side absorbs the surfactant composition and can make a reservoir effect and the hydrophobic polymer on the other side releases the surfactant composition.
[00153] A preferred hydrophilic polymer is a polymer comprising cellulosic units.
[00154] It is also preferred to use an aqueous surfactant composition as described above which comprises a monofunctional alcohol and a bifunctional alcohol, said monofunctional alcohol having preferably a lower molecular weight than said bifunctional alcohol.
[00155] Monofunctional alcohol comprises a single hydroxy group, typically ethanol or isopropyl alcohol. Bifunctional alcohol comprises only two hydroxy groups. An example of a particularly preferred bifunctional alcohol is propylene glycol (propane-1,2-diol).
[00156] The invention also relates to a damp non-cloth whose structure comprises a hydrophilic polymer, preferably a hydrophilic polymer comprising cellulosic units and a hydrophobic polymer, such cloth being impregnated by a composition containing a surfactant based on the compounds of formula (VIII) as previously described.
[00157] In another preferred embodiment, the application of the composition containing a surfactant in said precursor coating is done by cleaning the optical article coated with said precursor coating with a dry microfiber cloth, and said dry microfiber cloth was obtained by Impregnation, with a composition containing a surfactant based on the compounds of formula (VIII) as previously described from a microfiber cloth comprising microfibers made of polymers comprising polyester units and polyamide units, followed by a drying step.
[00158] The microfiber cloth used in the invention preferably comprises polyester microfibers and polyamide and / or microfibers that comprise a polyester / polyamide copolymer.
[00159] As is known in the art, a microfiber cloth or handkerchief is made of microfibers. A microfiber is a fiber with less than 1.3 Decitex (Dtex) per filament, preferably less than 1 Decitex per filament. Decitex is a measure of linear density and is commonly used to describe the size of a fiber or filament. Ten thousand meters of 1 decitex fiber weighs one gram. In a microfiber cloth, the fibers are combined to create threads, which are knitted or woven in a variety of constructions.
[00160] An example of a preferred microfiber cloth comprising microfibers made of polymers comprising polyester units and polyamide units is CEMOI ™ cloth (manufacturer: Company KB SEIREN - distributor: Facol) whose composition is 70% polyester / Nylon ™ 30% and which is commonly used to clean lenses. The microfiber cloth described above is usually impregnated by the composition containing the surfactant with the use of impregnation pad (s).
[00161] The purpose of the drying step in the preparation of the dry microfiber cloth is to remove the solvents present in the composition that contains surfactant. It is usually a heating step. The heating step preferably comprises heating to a temperature ranging from 60 ° C to 200 ° C, more preferably from 80 ° C to 150 ° C.
[00162] After the heating step, the microfiber cloth comprising microfibers made of polymers comprising polyester units and polyamide units is dried and the weight content of the surfactants of formula (VIII) that impregnate said microfiber cloth is preferably in a range of 10% to 45%, more preferably 14% to 40%, even better from 20 to 40% and optimally from 20% to 30% in relation to the total weight of the dry impregnated microfiber cloth (cloth and surfactant). In addition, the compounds of formula (VIII) in which y = 6 are present in an amount of at least 90% by weight, preferably at least 95%, more preferably 100% by weight, in relation to the weight of the compounds (VIII) in the impregnated microfiber cloth.
[00163] It has been determined that, surprisingly, the dry microfiber cloth comprising microfibers made of polymers comprising polyester units and polyamide units that has been impregnated by the composition containing surfactant based on the surfactants of formula (VIII) can it also removes stains from the surface of optical articles, while at the same time providing anti-fog properties with a long-lasting effect.
[00164] The invention also relates to a dry microfiber cloth which has been prepared by impregnation, with a composition containing a surfactant based on the compounds of formula (VIII), a microfiber cloth comprising microfibers made of polymers comprising units of polyester and polyamide units, followed by a drying step. Said dry microfiber cloth comprising microfibers made of polymers having polyester and polyamide units is thus impregnated with at least one surfactant of formula (VIII), wherein the compounds of formula (VIII) in which y = 6 are present in an amount of at least 90% by weight, preferably at least 95%, more preferably 100% by weight, in relation to the weight of the compounds (VIII) impregnated in the microfiber cloth.
[00165] The surfactant solution reduces the angle of static contact with water from the surface of the optical article, especially from a spectacle lens. The anti-fog coating of the invention preferably has a static contact angle with water less than or equal to 10 °, more preferably less than or equal to 5 °.
[00166] An immediately operational anti-fog coating is obtained as soon as the surfactant composition is applied, which represents one of the greatest advantages of the invention. Thus, it is not necessary to apply a surfactant solution often to score the anti-fog effect, as is the case with prior art products.
[00167] Additionally, the anti-fog effect provided by the anti-fog coating is long-lasting. This durability is tested during the fogging and defogging cycles, in a procedure described in the experimental section.
[00168] The anti-fog coating is temporary, but easily renewable, since a new application of the surfactant has to be carried out when there are no more sufficient surfactant molecules absorbed on the surface of the anti-fog coating precursor. The latter therefore remains "activable" in all circumstances.
[00169] The present invention also relates to a method for imparting anti-fog properties to an optical article, preferably a spectacle lens, which comprises the application of the composition containing a previously defined surfactant, which is preferably a liquid solution, on a main surface of said optical article and more preferably use a cloth or handkerchief impregnated with a surfactant composition based on the surfactants of formula (VIII) as described above and especially the wet non-cloth cloth or the dry microfiber cloth as described above.
[00170] Preferably, the main surface of the optical article on which said composition is applied has a static contact angle with water of 100 ° or less, preferably 90 ° or less, more preferably more than 10 ° and less than 50 °. Said main surface is generally the surface of a coating applied to the substrate of the optical article, for example, a precursor coating to an anti-fog coating. Preferably, said main surface is not the surface of a hydrophobic and / or oleophobic coating. Said main surface can be the uncoated surface of the substrate of the optical article.
[00171] In the present disclosure, a lens does not have anti-fog properties if it successfully passes the breath test. For this test, the tester places the lens to evaluate at a distance of about 2 cm from your mouth. The tester blows his breath on the exposed surface of the lens for 3 seconds. Tester can visually observe the presence or absence of a condensation distortion / opacity.
[00172] A lens is considered to have anti-fog properties if it inhibits the opacity effect that results from fogging at the end of the breath test (but it does not necessarily represent an anti-fog lens within the meaning of claim 1, as it may possibly have a visual distortion that leads to visual acuity <6/10).
[00173] Therefore, the method of the invention allows to provide anti-fog properties to any type of optical article, preferably spectacle lenses, whether the article has a precursor coating of anti-fog coating or not. The method is especially recommended for treating uncoated lenses or lenses only coated with an abrasion resistant coating, preferably of the type that contains polysiloxane.
[00174] The present invention finally relates to an optical article, preferably a lens for glasses, which comprises 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 its surface it is in direct contact with a precursor coating of anti-fog coating as defined above, and another part of the surface of said coating that comprises silanol groups on its surface, preferably the rest of its surface, is in direct contact with and adheres to a hydrophobic and / or oleophobic coating. These parts can be continuous or discontinuous.
[00175] Such an optical article can be used especially as a demonstrator to show the anti-fog properties, after application on the surface of it a liquid solution comprising at least one surfactant and / or a hydrophilic compound without any active surface properties such as previously defined, then, subjecting the article to conditions of fogging generation (breath, refrigerator, boiling water vapor ...) or subjecting its surface to one or more cleaning operations before being exposed to the conditions of fogging generation.
[00176] The optical article obscures that part of the surface covered with the hydrophobic and / or oleophobic coating and remains transparent in the area comprising the anti-fog coating.
[00177] Hydrophobic and / or oleophobic coatings or upper anti-dust coatings that can be used appropriately in that optical article are especially described in the application in WO 2010/055261. They differ naturally from the anti-fog coatings of the invention.
[00178] The hydrophobic and / or oleophobic coatings used preferably have a surface energy less than or equal to 14 mJ / m2, preferably less than or equal to 12 mJ / m2, in accordance with the method of Owens Wendt described in the article referred to in the application in WO2010 / 055261.
[00179] Such optical articles can be manufactured according to any of the methods disclosed in the document in WO 2011/080472, which is hereby incorporated by reference.
[00180] The following examples illustrate the invention in a more detailed, but not limiting way.
[00181] EXAMPLES 1. Used optical materials and articles
[00182] Silica is used in the form of granules supplied by the company Optron Inc .. The organosilane compound used in the examples to form the anti-fog coating precursor is 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane which comprises from 6 to 9 units of ethylene oxide, of formula (III) and with a molecular weight of 450 to 600 g / mol (CAS No .: 65994-07-2. Ref: SIM6492.7, supplied by the company Gelest, Inc.).
[00183] The lens used comprises a lens substrate in an ORMA® material, which comprises a polyurethane-based impact resistant primer with a thickness of about 1 micron, it is provided with an abrasion resistant coating with a thickness of about 3 microns by depositing and curing a composition as defined in Example 3 of EP 0614957, coated, in turn, with a 5-layer anti-reflective coating ZrO2 / SiO2 / ZrO2 / ITO / SiO2 (anti-reflective coating Y ) deposited in the abrasion-resistant coating by vacuum evaporation of the materials in the order in which they are mentioned (respective layer thickness: 29, 23, 68, 7 and 85 nm). An ITO layer is an electrically conductive layer of tin-enriched indium oxide (ln2O3: Sn).
[00184] These lenses are treated on both sides according to the methods described hereinafter, and the concave face is treated before the convex face.
[00185] In the examples, the anti-reflective coating is not subjected to any activation treatment before the deposition of the anti-fog coating precursor.
[00186] 2. Vapor deposition of the anti-fog coating precursor
[00187] In the examples, deposition is performed on the anti-reflective coating Y of a lens by evaporation under vacuum with the use of a heating source based on the Joule effect.
[00188] The siloxane compound of formula III is poured into a copper capsule (in the absence of any porous material) and this capsule is deposited on a conductive tantalum heating support. The evaporation device is a SATIS 1200 DLF or BALZERS BAK device. The evaporation pressure of the siloxane compound of formula III generally ranges from 5.10-10 MPa to 8.10-10 MPa (5.10-6 to 8.10-6 mbar) for SATIS 1200 DLF. Once evaporation is complete, the surface of each lens is rinsed with a little soapy water, optionally with isopropyl alcohol, then deionized water and cleaned with a dry Cémoi ™ tissue so that the excess siloxane compound of formula III deposited is removed.
[00189] The Cémoi ™ scarf is a scarf supplied by the supplier / distributor Facol under the reference Microfibre M840 S (30x40).
[00190] 3. Application of a liquid solution containing surfactant (temporary anti-fog solution)
[00191] 3.1 Preparation of surfactant solutions
[00192] Two different surfactants were used:
[00193] Capstone® FS 3100 is the surfactant used to prepare the surfactant solutions of the invention.
[00194] Capstone® FS 3100 is a surfactant comprising a compound of the general formula F (CF2) y- (CH2-CH2O) x + 1H (VIII) for which more than 90% by weight corresponds to the fraction y = 6 (still more than 95% by weight), x being an integer that is in a range from 1 to 14. In other words, Capstone® FS3100 is a mixture of compounds that have polyethoxylated chains of varying length, but a fluorinated chain of constant length (y = 6).
[00195] Capstone® FS3100 contains minute amounts of the compounds of formula (VIII) in which y is greater than 6 (as impurities) that are not detectable by HPLC. The distribution of the ethoxy group as determined by HPLC-MS in the mixture of Capstone® FS 3100 compounds is as follows:

[00196] Zonyl® FSO 100 (with DuPont) is used as a comparative surfactant. Zonyl® FSO 100 is a mixture of compounds of formula (VIII) in which y is equal to 6, 8 and 10 with weight amounts of approximately 65%, 30% and 5% respectively and x is an integer that is in a range from 2 to 13.
[00197] A solution is prepared for each surfactant: the surfactant is dissolved in a mixture of deionized water and isopropyl alcohol (IPA), in order to obtain an aqueous solution that contains 2.5% by weight of IPA and 6% by weight of surfactant.
[00198] 3.2. Deposition of the solution on the lenses
[00199] The lenses supplied with an anti-fog precursor coating prepared under 2 were treated using the solutions described under 3.1.
[00200] Each solution is applied as follows: 1. Shake the solution bottle before use. 2. Hold the lens between your thumb and index finger and apply two 2 droplets of the surfactant solution to the center of the convex face of the lens. 3. Use a clean Cémoi ™ tissue (Facol Microfibre M840 S supplier (30x40), spread the droplets with your fingertip over the entire lens surface without rubbing (maximum 7 seconds) 4. Perform the same operation with the face concave lens 5. Allow to dry for 5 to 10 seconds and control the lens, as for transmission only, under ambient light (ceiling light consisting of a neon tube), keeping the lens at a distance 30 to 50 cm from the eye 6. Using a clean Cémoi ™ handkerchief, wipe the edge of the lens 7. Remove the white marks that are visible on the transmission, the Cémoi ™ handkerchief being retained with the tip of the index finger, without rubbing strongly. The lens should be clean and without any white mark along its entire surface.
[00201] The method makes it possible to obtain a perfectly transparent ophthalmic lens.
[00202] 4. Hot steam test:
[00203] All vapor tests were performed on a panel with 10 lenses: 5 pairs (or doubles) of lenses, each pair comprising a lens according to the invention (lens treated with the solution with 6% by weight of Capstone® FS 3100) and a comparative lens (lens treated with the solution with 6% by weight of Zonyl® FSO 100).
[00204] Before the test, the lenses are placed for 24 hours in an environment of regulated temperature (20 to 25 ° C) and under 40 to 50% humidity.
[00205] For the test, the lenses are placed for 15 seconds above a heated container that contains water at 52 ° C. Immediately afterwards, a visual acuity scale located at a distance of 5 m is observed through the tested lens. The observer evaluates visual acuity as a function of time and according to the following criteria:
[00206] No fogging, no visual distortion (visual acuity = 10/10)
[00207] Blurring and / or visual distortion allowing visual acuity> 6/10
[00208] Blurring and / or visual distortion allowing visual acuity <6/10
[00209] In practical terms, to obtain a score of 0 or 1, a user who has a vision of 10/10 and who has placed the lens in front of his eye must be able to distinguish the orientation of the letters "E" on line 6/10 of the Snellen optotype table placed at a distance of 5 meters.
[00210] This text makes it possible to simulate the ordinary living conditions in which a user tilts his face towards a cup of tea / coffee or towards a pot filled with boiling water.
[00211] If the lenses obtain a score of 0 or 1, they are subjected to a new vapor test after having checked under a Waldmann lamp that they were completely dry.
[00212] The test is repeated for each pair of lenses until each lens obtains a score of 2, meaning that it failed the steam test.
[00213] The results are given in the following table (Table 1):

[00214] An improvement in the durability for the steam test can be noticed with the solution based on Capstone® FS-3100 for 3 to 4 of the 5 treated lenses (number of stress increased up to 40%), which is particularly important and amazing. For the other lenses, the performances of both surfactants are comparable.
[00215] 5. Tests under tropical and winter conditions
[00216] These tests were carried out using the system to determine the anti-fog performance of transparent optical articles which is fully described in French application application 11.53814 filed on May 4, 2011 and represented in Figure 1 of said application patent, in which it is designated (20).
[00217] A lens passes the test when obtaining a sharpness coefficient N> 0.6. A lens failed this test when obtaining a sharpness coefficient N <0.6. The sharpness coefficient N is defined in French application application 11.53814. a) Winter conditions
[00218] In this test, the lenses provided with an anti-fog precursor coating prepared under 2 and further treated as described in 3.2 using the solutions described under 3.1 (or with the commercial Defog it ™ solution) were stored for 60 minutes under " winter conditions "(4 ° C, 40% humidity) and were then quickly subjected to normal conditions (20 ° C, 50% humidity). The results are shown below: (Table 2)

[00219] b) Tropical conditions
[00220] In this test, the lenses supplied with an anti-fog precursor coating prepared under 2 and further treated using the solutions described under 3.1 (or with the commercial Defog it ™ solution) were stored for 30 minutes under normal conditions (20 ° C, 50% humidity) and were then quickly subjected to “tropical conditions” (30 ° C, 70% humidity). The results are shown below:

[00221] Table 3
[00222] It can be concluded from these two test series that Capstone® FS-3100 (6% by weight) is superior to Zonyl® FSO-100 (6% by weight) in terms of anti-fog performance and comparable to the commercial solution Defog it ™.
[00223] 6. Durability of the anti-fog effect after mechanical stress (after the application of a surfactant solution)
[00224] This test allows to evaluate the resistance to cleaning of the temporary anti-fog solution on the surface of the lenses. The same was performed on several pairs of lenses (2 lenses). The general test protocol is described in § 5 of the experimental part of WO 2011/080472.
[00225] Each pair of lenses initially submitted to a series of 5 cleanings, then 10, 10, 10, 20, 20 and 20 additional cleaning operations were performed. In summary, a hot steam test followed by a drying step is performed between each cleaning series. The test was generally stopped when at least one lens from a pair yielded a low score.
[00226] Here, a cleaning operation corresponds to a moderately marked rotation of a CémoiTM cleaning wipe on both sides of the lens (the lens is pressed between the thumb and the index finger).
[00227] The anti-fog scores (A, B, C or D) correspond to the haze level at the end of each hot steam test, after the implementation of the corresponding number of cleaning operations (accumulated number):
[00228] A: Homogeneous water film (acuity 10/10)
[00229] B: Visual distortion considered acceptable by the user
[00230] C: Visual distortion considered as not acceptable by the user (heterogeneous water film)
[00231] D: White widespread opacity, fine water droplets.
[00232] The lenses are considered to have successfully passed the durability test if they have obtained an A or B score.
[00233] G1 lenses are lenses according to claim 1 that have an anti-reflective coating and a precursor coating to an anti-fog coating. G1 lenses are supplied with a precursor coating of anti-fog coating prepared under 2 and further treated as described in 3.2 using the solutions described under 3.1 or similar solutions with a smaller amount (3% by weight) or greater (15% by weight) of surfactant, keeping the amount of 2.5% isopropyl alcohol.
[00234] G2 lenses are lenses without anti-reflective coating and without precursor coating of an anti-fog coating. G2 lenses are identical to those described in § 1, except that no anti-reflective coating has been deposited on the abrasion resistant coating. The solutions described under 3.1 were deposited directly on said abrasion resistant coating, as described in 3.2.
[00235] The results are shown in the tables below:


[00236] Table 4

[00237] Table 5
[00238] For G1 lenses, it can be seen that the durability of the anti-fog performance of Capstone® FS-3100 at 3% by weight after mechanical stress is almost equivalent to that of Zonyl® FSO-100 at 6% by weight. Both surfactants exhibit similar anti-fog performance when used at a weight content of 6%.
[00239] For G2 lenses, Capstone® FS-3100 is more effective than Zonyl® FSO-100 at a weight content of 6%. However, the durability of the anti-fog effect is less due to the absence of the precursor coating of an anti-fog coating on G2 lenses.
[00240] 7. Evaluation of additional lenses and cosmetic appearance of the lenses
[00241] The G1 lens is the lens according to claim 1 which was defined in § 6. The G3 lens is the anti-fog glasses lens marketed with Seiko, which comprises a substrate that has a refractive index of 1.6 and a precursor coating to an anti-fog coating. The G4 lens is the anti-fog glasses lens marketed with Tokai, which comprises a substrate that has a refractive index of 1.6 and a precursor coating to an anti-fog coating.
[00242] G1, G3 and G4 lenses were further treated as described in 3.2 using the solution described under 3.1 which comprises 6% by weight of Capstone® FS-3100.
[00243] They were subjected to a hot steam test as described previously (without cleaning cycles), dried as in § 6 and then subjected to the hot steam test / drying cycles. Anti-fog scores were given to the lenses after each hot steam test. The results are shown in the table below (Table 6).

[00244] All G1, G3 and G4 lenses after being treated as described in 3.2 using the solution described under 3.1 which comprises 6% by weight of Capstone® FS-3100 exhibit anti-fog properties.
[00245] The G4 lens does not exhibit satisfactory anti-fog durability with the Capstone® FS-3100 solution. The distortion is observed quickly and the cosmetic aspect after fogging is not acceptable. In fact, the lens looks whitish after the deposition of the surfactant solution. After drying to evaporate the water film formed on the lens surface, spots appear.
[00246] G1 and G3 lenses demonstrate anti-fog performance comparable to Capstone® FS-3100 solution. However, unlike the G1 lens, the cosmetic aspect after the fogging of the G3 lens is not acceptable. After drying to evaporate the water film formed on the lens surface, spots appear.
[00247] The G1 lens did not exhibit cosmetic problems, before and after the elimination of excess siloxane compound of formula III, although several cleaning cycles are performed in a durability test. After depositing the surfactant solution, the ability of a tissue to slip on the surface of this lens was satisfactory and was the same using Zonyl® FSO-100 6% by weight instead of Capstone® FS-3100 6% by weight. In addition, the evaporation rate of the water film formed on the lens surface after fogging was the same for both surfactants. In both cases, the homogeneity of the water film was the same.

权利要求:
Claims (20)
[0001]
1. Optical article comprising a substrate that has at least one main surface coated with a first coating and, in direct contact with that first coating, a coating precursor of an anti-fog coating, characterized by the fact that the coating precursor of the coating anti-fogging: - it is obtained by grafting at least one organosilane compound that has: a polyoxyalkylene group; and at least one silicon atom that has at least one hydrolyzable group, - and is additionally coated with a film obtained by applying a surfactant-containing composition to the said precursor containing a surfactant containing at least one surfactant of formula F (CF2) y - (CH2-CH2O) x + 1H (VIII), where x is an integer that is in a range from 1 to 14, y is an integer less than or equal to 10, compounds of formula (VIII) in which y = 6 is present in an amount of at least 90% by weight, based on the weight of the compounds (VIII) present in the composition, in order to form an anti-fog coating.
[0002]
2. Optical article, according to claim 1, characterized by the fact that the surfactant-containing composition is a liquid solution.
[0003]
Optical article according to any one of claims 1 to 2, characterized in that the compounds of formula (VIII), in which x is in a range of 1 to 4, are present in an amount of at least 50 % by weight, based on the weight of the compounds (VIII) present in the surfactant-containing composition.
[0004]
4. Optical article according to any one of claims 1 to 3, characterized by the fact that the composition containing surfactant comprises from 0.5 to 15% by weight of surfactants of formula (VIII), in relation to the weight of said composition.
[0005]
Optical article according to any one of claims 1 to 4, characterized in that the compounds of formula (VIII), in which y is greater than 6, are present in an amount of at least 5% by weight, in relation to the weight of the compounds (VIII) present in the composition that contains surfactant.
[0006]
Optical article according to any one of claims 1 to 5, characterized in that the first coating comprises silanol groups on its surface.
[0007]
Optical article according to any one of claims 1 to 6, characterized in that the first coating is an anti-reflective coating, an abrasion resistant coating or a silica-based layer deposited in an abrasion resistant coating.
[0008]
Optical article according to any one of claims 1 to 7, characterized in that the coating precursor of the anti-fog coating has a thickness less than or equal to 5 nm.
[0009]
Optical article according to any one of claims 1 to 8, characterized in that the coating precursor of the anti-fog coating has a static contact angle with water of more than 10 ° and less than 50 °.
[0010]
10. Optical article according to any one of claims 1 to 9, characterized in that the organosilane compound is a compound of the formula: R1YmSi (X) 3-m (I) in which the Y groups, which are the same or different, are monovalent organic groups linked to silicon through a carbon atom, groups X, which are the same or different, are hydrolyzable groups, R1 is a group comprising a polyoxyalkylene group and is an integer equal to 0.1 or 2.
[0011]
Optical article according to any one of claims 1 to 10, characterized in that the organosilane compound has a polyoxyalkylene group comprising 5 to 20 carbon atoms.
[0012]
Optical article according to any one of claims 1 to 11, characterized in that it is additionally defined as an ophthalmic lens.
[0013]
13. Method for imparting anti-fog properties to an optical article characterized by the fact that it has at least one main surface, which comprises the application on said main surface of a composition containing surfactant, as defined in any one of claims 1 to 0.
[0014]
14. Method according to claim 13, characterized in that the application on said main surface comprises cleaning said main surface with a non-woven cloth, the structure of which comprises a hydrophilic polymer and a hydrophobic polymer, said cloth being is impregnated with said composition that contains surfactant.
[0015]
15. Method according to claim 14, characterized in that the hydrophilic polymer comprises cellulosic units.
[0016]
16. Method according to claim 13, characterized in that the application on said main surface comprises cleaning said main surface with a dry microfiber cloth obtained by impregnating, with said surfactant-containing composition, a fabric of microfiber comprising microfibers produced from polymers comprising polyester units and polyamide units, followed by drying said microfiber fabric.
[0017]
17. Method according to any one of claims 13 to 16, characterized in that the main surface of the optical article has a static contact angle with water of 100 ° or less, before applying said composition containing surfactant .
[0018]
18. Method according to any one of claims 13 to 17, characterized in that the optical article comprises a substrate that has at least one main surface coated with a precursor of coating an anti-fog coating, and in which the precursor of coating of the anti-fog coating is obtained by grafting at least one organosilane compound that has: 1. a polyoxyalkylene group, and 2. at least one silicon atom that bears at least one hydrolyzable group,
[0019]
19. Wet non-woven cloth whose structure comprises a hydrophilic polymer, characterized by the fact that it comprises cellulosic units and a hydrophobic polymer, the cloth being impregnated by a composition containing a surfactant, as defined in any one of claims 1 to 5.
[0020]
20. Dry microfiber cloth, characterized in that it is obtained by impregnation, with a composition containing a surfactant, as defined in any one of claims 1 to 5, of a microfiber fabric comprising microfibers made of polymers comprising polyester units and polyamide units, followed by drying said microfiber fabric.

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同族专利:

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公开号 | 公开日

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BR112014001458A2|2017-02-21|

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KR20140058498A|2014-05-14|

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JP2014521123A|2014-08-25|

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JP6336387B2|2018-06-06|

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AU2012289095B2|2015-08-27|

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KR101961392B1|2019-03-25|

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AU2012289095A1|2014-02-20|

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WO2013013929A1|2013-01-31|

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JP2018097372A|2018-06-21|

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CA2842290A1|2013-01-31|

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CN103718064B|2015-12-09|

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US20140177053A1|2014-06-26|

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US9645285B2|2017-05-09|

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ZA201400427B|2014-11-26|

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CA2842290C|2019-09-24|

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EA201400048A1|2014-04-30|

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NZ619974A|2016-01-29|

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CN103718064A|2014-04-09|

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EA026288B1|2017-03-31|

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法律状态:
2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2020-03-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-07-28| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2020-12-22| B09A| Decision: intention to grant|

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2021-03-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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FR1156704|2011-07-22|

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FR1156704|2011-07-22|

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EP2011063635|2011-08-08|

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EPPCT/EP2011/063635|2011-08-08|

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PCT/EP2012/062620|WO2013013929A1|2011-07-22|2012-06-28|Optical article comprising a surfactant-based temporary antifog coating with an improved durability|

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