OPTICAL ARTICLE UNDERSTANDING A PRECURSING COATING OF AN ANTI-DAMAGING COATING AND A TEMPORARY LAYER

专利摘要:
OPTICAL ARTICLE UNDERSTANDING A PRECURSING COATING OF AN ANTI-DAMAGING COATING AND A TEMPORARY LAYER MAKING IT SUITABLE FOR EDGING The present invention relates to an optical article, preferably an ophthalmic lens comprising a substrate on which at least one main surface is coated with an coating that has silanol groups on its surface, and in direct contact with the coating, a precursor coating of an anti-fog coating, the precursor coating of the anti-fog coating being formed by deposition, on the coating containing silanol groups of at least one compound A having a polyoxyalkylene group and at least one group capable of establishing a covalent bond with a silanol group, wherein the precursor coating of the anti-fog coating comprises an inner portion in which said compound A is grafted into a coating containing silanol groups on the surface, and an outer portion eliminating washable and / or cleaned, resulting from the deposition of compound A, the precursor coating of the anti-fog coating to be coated with at least a temporary layer, comprising at least 50% by mass of silica, based on the total mass of the layer temporary. Such an article is made suitable for (...).
公开号:BR112013029191B1
申请号:R112013029191-5
申请日:2012-05-11
公开日:2020-12-29
发明作者:Francis Henky；Alexis Theoden
申请人:Essilor International；
IPC主号:

专利说明:

[0001] The present invention is useful for edging or cutting an optical article, more particularly an ophthalmic lens, coated with a coating comprising silanol groups on its surface, in which the surface has been modified in order to allow an effective and lasting application of a temporary anti-fog solution. The present invention relates to such an article developed to suit the edging, a preparation process and an edging process of said article.
[0002] Various supports, such as plastic materials and glass, have the inconvenience of being covered by a mist as the temperature of its surface drops below the dew point of the ambient air. This is clearly the case with the glass that is used to build glasses for transport vehicles or buildings, mirrors, ophthalmic lenses such as glasses, etc. The formation of fog on these surfaces results in a decrease in transparency, due to the diffusion of light by water droplets, which can be a significant nuisance.
[0003] To avoid the formation of fog in a very humid environment, ie, the condensation of tiny droplets of water on a support, it is possible to deposit hydrophilic coatings on the external surface of said support, with a reduced angle of static contact with the water (typically 10 ° or less). Such permanent anti-fog coatings with hydrophilic properties, resulting in hydrophilic compounds permanently attached to another coating or support, acting with sponges in relation to the mist and allowing the water droplets to stick to the surface of the support forming a very thin film, transmitting a sensation transparency. Such coatings, due to water absorption, swell, soften and become less mechanically resistant.
[0004] Another solution, to combine the anti-reflective and anti-fog properties, is to use a thin and porous layer with a reduced index of refraction, consisting in part of surfactants, allowing the layer to acquire permanent anti-fog properties.
[0005] The anti-fog properties can also be obtained by applying the temporary commercial solutions, available in the form of vaporizer or wipes, on the lens glasses acting as an outer layer, an anti-dirt coating (hydrophobic or oleophobic) ). They allow to obtain the anti-fog property in a short period of time, because after passing with a few wipes these hydrophilic materials are removed.
[0006] A more interesting solution is to obtain an anti-fog coating by applying a temporary hydrophilic solution to the surface of a precursor coating to an anti-fog coating, representing an alternative to permanent anti-fog coatings.
[0007] French patent application No. 10,53269 describes the deposition on the outer surface of an optical article coated with a coating containing silanol groups on its surface, a hydrophilic coating precursing an anti-fog coating obtained by grafting a organosilane compound having a polyoxyalkylene group and at least one silicon atom having at least one water-soluble group. The anti-fog coating itself, which is a temporary coating, is obtained after application to the surface of a precursor coating of a surfactant. The precursor coating of the anti-fog coating is typically less than or equal to 5 nm thick. This final thickness can be obtained by directly depositing the appropriate amount of the organosilane compound.
[0008] However, the inventors have found that it is preferable to form the precursor coating of an anti-fog coating by depositing an excess of organosilane compound on the surface of the coating containing silanol groups and eliminating the excess of that deposited but not grafted compound, in order to achieve the same final thickness. The inventors have found that when a layer of grafted organosilane compound is formed directly, having a thickness that does not require the elimination of excess organosilane compound, we can in certain circumstances obtain an irregular deposit and a precursor coating of the anti-fog coating whose surface does not have a sufficient affinity for a liquid surfactant solution, which leads to a coating that lacks the desired anti-fog properties, which is generally less durable. Such reproducibility problems must be avoided in order to industrialize the production process.
[0009] The last stage of finishing an optical article such as an ophthalmic lens is the beading or cutting operation, which consists of producing the fraction or the periphery of the lens in order to conform to the dimensions required to adapt the lens to the eyeglass frame for which it was produced.
[0010] The grinding is generally carried out on a grinder comprising a diamond grinder that performs the machining as defined above. The lens is held, during this operation, by the locking organs that intervene in an axial orientation. The relative movement of the glass in relation to the emery is controlled, generally in numerical terms, in order to achieve the desired shape. As demonstrated, it is of course imperative that the lens is kept firmly immobilized.
[0011] To do this, before the overhang operation, a lens locking operation is performed, i.e., a means of support or adhesion is positioned on the convex surface of the lens. Typically, a maintenance support (or fixation support), such as a self-adhesive insert, for example, a double-sided adhesive support, is placed between the adhesion pad and the convex surface of the lens. The adhesion block that adheres to the lens by means of an adhesive support is thus mechanically fixed on the grinding wheel of the grinder and an axial arm blocks the lens by applying a central force on the face of the lens opposite the adhesion block. When machining, a tangential cutting force is generated on the lens, which can generate a rotation of the lens in relation to the adhesion block if the lens maintenance system is not sufficiently effective. The good maintenance of the lens depends mainly on the good adhesion with the interface of the maintenance support / convex surface of the lens.
[0012] The optical articles comprise a hydrophobic and / or lipophobic anti-dirt outer layer, typically based on fluorosilane-type materials, which have a reduced surface energy (typically less than 14 mJ / m2 and generally less than or equal to 12 mJ / m2), cannot be edged directly because the adhesion to the interface support / convex surface is altered, making satisfactory edging operations difficult.
[0013] Surface energies are measured according to the Owens Wendt process (Estimation of the surface force energy of polymers Owens D.K., Wendt R.G. (1969) J. APPL. POLYM. SCI, 13, 1741-1747).
[0014] When flanging, the lens must not shift more than 2 °, preferably at most 1 ° and, consequently, the block's adhesion on the lens surface is essential to obtain a satisfactory flange. The consequence of sliding the lens in the course of a poorly conducted beading operation is the pure and simple loss of the lens.
[0015] To remedy such difficulties in refining the lenses provided with a hydrophobic and / or lipophobic external coating, it was proposed to form a temporary coating on these coatings, of an organic or mineral nature, in particular a temporary layer of MgF2, detachable coatings of a nature polymeric or temporary adhesive films of a polymeric nature. These temporary layers are described in particular in applications EP 1392613, EP 1633684, WO 2005/015270, WO 03/057641, JP 2004-122238, WO 03/092957.
[0016] The inventors have found that it is difficult to embellish an optical article comprising as an outer layer an anti-fog coating precursor deposited in excess, ie, where the thickness is greater than that of a grafted layer, although that layer has a high surface energy . Such a layer does not allow a good performance of the block and results in the article sliding during the beading operation.
[0017] The objective of the present invention is the preparation of an optical article, comprising a precursor coating of the anti-fog coating, of thickness preferably greater than 3 nm, which is suitable for the overhang.
[0018] The invention also aims to develop a method of reframing optical articles coated with a precursor coating of the anti-fog coating, which is reliable and guarantees a very high success rate for the finishing operation, allowing to avoid all problems with sliding of the lens during the beading operation in question.
[0019] At the origin of the invention, the inventors demonstrated that the problem found when refining the optical articles mentioned below results in fact from the deposition of an excess of the precursor of the anti-fog coating. We could think that the problem can be solved by completely eliminating the excess of the precursor compound from the deposited anti-fog coating before proceeding with the finishing. This solution is by no means industrially satisfactory, because the elimination operation requires a thorough cleaning of the surface of the optical article so that the overhang can be correctly carried out, which is technically complex. The use of adhesive films (called self-adhesive films, in the case of smaller films, larger than the size of the adhesive support and less than the diameter of the glass) disposed between the hydrophilic layer and the adhesive support to improve the stability of said support, is also not satisfactory . This causes an additional cost for the optometrist and handling problems for the optometrist because the deposition of a sticker without forming a fold on its surface is a delicate operation.
[0020] The objectives of the invention are achieved through the use of a temporary layer whose composition is specially designed to solve the problem posed, which interposes between the precursor coating of the excess deposited anti-fog coating and the fixing member and must be eliminated after the overhaul operation.
[0021] Thus, the present invention relates to an optical article comprising a substrate in which at least one of the main surfaces is coated with a first coating comprising silanol groups on its surface and, in direct contact with that coating, a second coating, precursor of an anti-fog coating, the second coating, precursor of an anti-fog coating, being formed by deposition on the first coating, comprising on its surface silanol groups with at least one compound A containing: a polyoxyalkylene group, and at least , a group capable of establishing a covalent bond with a silanol group,
[0022] in which the second coating, precursor of the anti-fog coating, comprises an internal part in which said compound A is grafted into a coating comprising on its surface silanol groups and an external part eliminable by washing and / or drying, resulting from deposition of compound A, the second coating, precursor to the anti-fog coating being coated by at least one temporary layer comprising at least 50%, preferably at least 60%, more preferably at least 70% by mass of silica, relative to the mass total temporary layer.
[0023] The invention also concerns a manufacturing process and an edging process for such an article.
[0024] In the present patent 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 on top of the substrate / coating, ( ii) is not necessarily in contact with the substrate / coating, ie, one or more intermediate coatings may be arranged between the substrate / coating and the coating in question (however, it is preferable to be in contact with said substrate / coating) and ( iii) does not necessarily cover the substrate / coating completely. When "a layer 1 is located under a layer 2" it is understood that layer 2 is further away from the substrate than layer 1. Likewise, a layer called "external" is further away from the substrate than a layer said " internal ".
[0025] "Anti-fog coating" means, within the scope of the present patent application, a coating that, when a transparent glass substrate, coated with such a coating, is placed in conditions of generating a mist on said substrate not equipped with the said coating, it immediately allows a visual acuity> 6/10 ° for an observer who sees through the coated glass on a visual acuity scale located 5 meters away. A test allowing to evaluate the anti-fog properties of a coating is described in the experimental part. In fog-generating conditions, anti-fog coatings may not present fog on their surface (without visual distortion in the ideal situation, or visual distortion but visual acuity> 6/10 ° in the measurement conditions indicated below), presenting the fog at their surface but still allowing, despite the disturbance of visibility caused by fogging, a visual acuity> 6/10 ° under the measurement conditions indicated below. A non-fogging coating does not allow visual acuity> 6/10 ° as it is exposed to conditions of mist generation and generally has a condensation veil in the measurement conditions indicated below.
[0026] "Anti-fog glass" means, within the scope of this application, a glass equipped with a "anti-fog coating" as defined below.
[0027] Thus, the precursor of the anti-fog coating according to the invention, which is a hydrophilic coating, is not considered to be an anti-fog coating within the scope of the invention. In fact, such a precursor to the anti-fog coating does not allow visual acuity> 6/10 ° under the measurement conditions indicated below.
[0028] By temporary anti-fog coating, is meant an anti-fog coating obtained after the application of a liquid solution containing at least one surfactant to the surface of a precursor coating of said anti-fog coating. The durability of a temporary anti-fog coating is generally limited by wiping its surface, the surfactant molecules are not permanently attached to the surface of the coating, but are simply adsorbed more or less in a lasting way.
[0029] The optical article prepared according to the invention comprises a substrate, preferably transparent, having front and rear main faces, at least one of said main faces comprising a coating containing silanol groups on its surface, preferably the two main faces . By the back face (usually concave) of the substrate, we mean a face that, when using the article, is the closest to the wearer's eyes. Conversely, the front face (usually convex) of the substrate means the face that, when using the article, is the furthest from the wearer's eyes.
[0030] Although the article according to the invention may be any optical article susceptible to being confronted with a mist formation, such as a monitor, a glazing for the automotive or construction industry, or a mirror, a lens is preferred optics, more preferably an ophthalmic lens, for glasses, or an outline of an optical or ophthalmic lens.
[0031] This excludes articles such as intraocular lenses in contact with living tissues or contact lenses, which are not intrinsically confronted with the problem of fogging, unlike glasses lens glasses.
[0032] The coating containing on its surface silanol groups of the invention can be formed on at least one of the main faces of an empty substrate, ie, uncoated, or on at least one of the main faces of a substrate already coated with a or more functional coatings.
[0033] The substrate of the optical article according to the invention can be mineral or organic glass, for example an organic glass in thermoplastic or thermoset plastic material.
[0034] Particularly preferred classes of substrates are poly (thiourethanes), polyepisulfides and resins resulting from the polymerization or (co) polymerization of alkyleneglyco bis-allylcarbonates. The latter are sold, for example, under the trade name CR-39® by the company PPG Industries (ORMA® ESSILOR lenses).
[0035] In certain applications, it is preferable that the main surface of the substrate is coated with one or more functional coatings, prior to deposition of the coating containing silanol groups on its surface. Such functional coatings classically used in optics can be, without limitation, a first anti-shock layer, an anti-abrasive and / or anti-scratch coating, a polarized coating, a photo-chrome coating or a colored coating, in particular a first anti-shock layer coated with an anti-abrasion and / or anti-scratch layer.
[0036] The coating containing silanol groups on its surface can be deposited on an anti-abrasion and / or anti-scratch coating. The anti-abrasion and / or anti-scratch coating can be any layer classically used as anti-abrasion and / or anti-scratch coating in the field of ophthalmic lenses.
[0037] Abrasion and / or scratch resistant coatings are preferably hard coatings based on poly (meth) acrylates or silanes generally comprising one or more mineral fillers intended to increase the hardness and / or refractive index of the coating , once hardened. By (meth) acrylate is meant an acrylate or a methacrylate.
[0038] Among the coatings recommended in the present invention, coatings based on epoxysilane hydrolysates, such as those described in EP 0614957, US 4,211,823 and US 5,015,523, can be mentioned.
[0039] The thickness of the anti-abrasion and / or anti-scratch coating generally ranges from 2 to 10 μm, preferably from 3 to 5 μm.
[0040] Before the deposition of the anti-abrasion and / or anti-scratch coating, it is possible to deposit on the substrate a coating for the primary improvement of shock resistance and / or adhesion of the subsequent layers in the final product.
[0041] Such a coating can be any primary anti-shock layer classically used for articles in transparent polymeric material, such as that of ophthalmic lenses.
[0042] Among the preferred primer compositions, thermoplastic polyurethane-based compositions, such as those described in JP 63-141001 and JP 63-87223, the poly (meth) acrylic primer compositions, such as those described in US application 5,015,523, compositions based on thermoset polyurethanes, such as those described in application EP 0404111 and compositions based on poly (meth) acrylic latex or polyurethane type latex, such as those described in US applications 5,316,791 and EP 0680492.
[0043] The primary layers generally have thicknesses, after hardening, of 0.2 to 2.5 μm, preferably 0.5 to 1.5 μm.
[0044] The coating comprising silanol groups on its surface will be described below. By coating comprising silanol groups on its surface, is meant a coating that naturally has silanol groups on its surface, or a coating whose silanol groups were created after undergoing a surface activation treatment. Such a coating is therefore a coating based on siloxanes or silica, for example, without limitation, a layer of silica, a sol-gel coating, based on, inter alia, organosilanes such as alkoxysilanes or a coating based on silica colloids. It may include, in particular, an anti-abrasive and / or anti-scratch coating or, according to a preferred embodiment, a mono-layer anti-reflective coating or a multi-layer anti-reflective coating, the outer layer of which has silanol groups on its surface. An outer layer in a stack means the layer furthest from the substrate.
[0045] The surface activation treatment eventually employed to create silanol groups or at least increase their proportion on the surface of a coating, is generally carried out under vacuum. It can consist of bombardment with energetic and / or reactive species, for example an ion beam (“Ion Pre-Cleaning” or “IPC”) or an electron beam, from a treatment by crown discharge, by laser fragmentation, a UV treatment, or a vacuum plasma treatment. It can also consist of an acid or alkaline and / or solvent surface treatment. Many of these treatments can be combined.
[0046] Energetic (and / or reactive) species means, in particular, ionic species containing an energy 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 ionic, radicals, or species such as photons or electrons.
[0047] The coating containing silanol groups on its surface is preferably a layer with a reduced index of refraction based on silica (comprising silica), ideally consisting of a layer of silica (SiO2), usually obtained by deposition in the vapor phase . Said silica-based layer is preferably less than or equal to 500 nm in thickness, more preferably from 2 to 110 nm, preferably ranging from 5 to 100 nm.
The coating containing silanol groups on its surface preferably comprises at least 70% by weight of SiO2, more preferably at least 80% by weight and even more preferably 90% by weight of SiO2. As already mentioned, in an optimum embodiment, it comprises 100% by mass of silica.
[0049] The coating containing silanol groups on its surface may also be a silane-based sol-gel coating, such as alkoxysilanes, for example tetraethoxysilane, or organosilanes, such as Yglycidoxypropyltrimethoxysilane. Such a coating is obtained by liquid deposition, using a liquid composition containing a silane hydrolyzate and eventually colloidal materials with a high refractive index (> 1.55, preferably> 1.60, more preferably> 1.70) or reduced (<or = to 1.55). Such a coating whose layers comprise an organic / inorganic hybrid matrix based on silanes in which the colloidal materials are dispersed allowing to adjust the refractive index of each layer, is described for example in application FR 2858420.
[0050] According to an embodiment of the invention, the coating containing silanol groups on its surface is a silica-based layer deposited on an anti-abrasive coating, preferably directly deposited on said anti-abrasive coating.
[0051] According to another embodiment of the invention, which is the preferred embodiment, the optical article according to the invention contains an anti-reflective coating. When such a coating is present, it generally constitutes the coating containing silanol groups on its surface within the scope of the invention. Said anti-reflective coating can be any anti-reflective coating classically used in the field of optics, in particular ophthalmic optics, provided that it contains silanol groups on its surface.
[0052] 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. It allows to reduce the reflection of light at the article / air interface over a relatively wide portion of the visible spectrum.
[0053] As is also well known, anti-reflective coatings classically comprise mono-layer or multi-layer stacking of dielectric materials. They are preferably multi-layer coatings, comprising layers with a high refractive index (HI) and layers with a low refractive index (BI).
[0054] In the present application, a layer of the anti-reflective coating is said layer of high refractive index with its refractive index 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 layer of low refractive index with its refractive index being 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, for a wavelength of 550 nm.
[0055] The HI and BI layers are, respectively, the classic high refractive index and low refractive index layers, well known in the art, whose constitution, thickness and deposition mode are described in detail in WO 2010/109154 .
[0056] 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.
[0057] Before the formation of the precursor of the anti-fog coating on the coating containing silanol groups on its surface, it is common to subject the surface of said coating to a physical or chemical activation treatment, designed to increase the adhesion of the precursor of the anti-coating. - fog. These treatments can be chosen from those described above for the activation of the coating comprising silanol groups on its surface.
[0058] According to the invention, the coating containing silanol groups on its surface is directly in contact with the precursor coating of the anti-fog coating, which will now be described.
[0059] "Precursor to an anti-fog coating" means within the scope of the present invention a coating that, upon application on its surface of a liquid solution containing a surfactant to form a film, constitutes an anti-fog coating within the scope of the invention. The set consisting of the precursor coating and the film of the surfactant-based solution constitutes the anti-fog coating itself.
[0060] The precursor coating of the anti-fog coating is formed by depositing, in sufficient quantity, on the coating containing on its surface silanol groups, of at least one compound A having a polyoxyalkylene group and at least one group capable of establishing a bond covalent with a silanol group. According to the invention, the deposition of compound A forms a precursor coating to an anti-fog coating, comprising an inner part in which said compound A is grafted into the coating containing silanol groups on its surface, permanently (and not by adsorption) and an external part that can be washed and / or dried.
[0061] To achieve such a structure, it is necessary to deposit an excess of compound A on the surface of the coating containing silanol groups. The definition of the deposition parameters to achieve such a configuration is at the discretion of the person skilled in the art.
[0062] Excess means an amount of compound A greater than the amount that will be required to form a layer of compound A grafted onto the surface of the coating containing silanol groups.
[0063] Thus, the precursor coating of the anti-fog coating is a coating preferably containing a thickness greater than or equal to 3 nm, more preferably> 5 nm, even more preferably> 8 nm, and ideally> 10 nm. Its thickness is preferably less than 100 nm, more preferably <50 nm and even more preferably <20 nm. It typically ranges from 3 to 100 nm, preferably from 5 to 50 nm.
[0064] The outer part of the precursor coating of the anti-fog coating is removable by washing and / or wiping, meaning that it would be eliminated and subjected particularly to a wash with water containing soap (including a surfactant) through a sponge and then with deionized water, and / or wiping for typically 20 seconds or less, through a dry or eventually impregnated CEMOI ™, Wypall ™ or Selvith ™ fabric, typically with isopropyl alcohol. Such wiping can eventually be followed by a new wash with deionized water and a final wipe with a cloth.
[0065] Compound A is able, thanks to its or its reactive group (s), to establish a covalent bond with the silanol groups present on the surface of the coating on which it is deposited. Such a group may be, without limitation, an isocyanate, acrylate, methacrylate, halogenoalkyl, carboxylic or sulfonic acid group, acyl chloride, chlorosulfonyl, chloroformate, ester, a silicon atom carrying at least one hydrolyzable group, or a hydrolyzable group containing an epoxide function such as the glycidyl group, preferably a silicon atom carrying at least one hydrolyzable group.
[0066] Compound A is preferably an organosilane compound whose group (s) capable of establishing a covalent bond with a silanol group is (are) a silicon atom (s) bearing at least a hydrolyzable group. Its polyoxyalkylene chain is functionalized at a single end or at both ends, preferably at a single end, by at least one, preferably a single, group containing at least one silicon atom carrying at least one hydrolyzable group . Said organosilane compound preferably comprises a silicon atom bearing at least two hydrolyzable groups, preferably three hydrolyzable groups. Preferably, it does not comprise the urethane group. It is preferably a compound of the formula: R1YmSi (X) 3-m (I)
[0067] where groups Y, identical or different, are monovalent organic groups linked to silicon by a carbon atom, groups X, identical or different, are hydrolyzable groups or hydroxyl groups, R1 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 groups alkoxy -O-R3, in particular alkoxy at C1-C4, acyloxy -OC (O) R4 where R4 is an alkyl radical, preferably at C1-C6, preferably methyl or ethyl, halogens such as Cl and Br or trimethylsiloxy (CH3) 3SiO-, and combinations of these groups. Preferably, the groups X are alkoxy groups, in particular methoxy or ethoxy and, more preferably, ethoxy.
The group Y, present when m is not null, is preferably a hydrocarbon group, saturated or not, preferably in C1-C10 and more preferably in C1-C4, for example an alkyl group, such as methyl or ethyl , a vinyl group, an aryl group, for example phenyl, optionally substituted, particularly by one or more C1-C4 alkyl groups. Preferably, Y represents the methyl group.
[0070] According to 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. The R1 group preferably checks the same conditions.
[0072] The group R1 generally has the formula -L-R2, where L is a divalent group attached to the silicon atom of the compounds of formula I or II by a carbon atom, and R2 is a group comprising a polyoxyalkylene group attached to the group L by an intermediate of an oxygen atom, said oxygen atom being included in the group R2. Non-limiting examples of the L groups are the linear or branched alkylene groups, optionally substituted, cycloalkylene, arylene, carbonyl, starch, or combinations of these groups such as the cycloalkylene alkylene, biscicloalkylene, biscicloalkylene alkylene, arylene alkylene, bisphenylene, bisphenylene alkylene, alkylene starch, being an example is the CONH (CH2) 3 group, or the -OCH2CH (OH) CH2e -NHC (O) - groups. Preferred L groups are alkylene groups, preferably linear, preferably containing 10 carbon atoms or less, more preferably 5 carbon atoms or less, for example ethylene and propylene groups.
Preferred R2 groups comprise a polyoxyethylene (CH2CH2O) n-, polyoxypropylene group, or combinations of those groups.
Preferred organosilanes of formula I are the following compounds of formula II: Ym (X) 3-mSi (CH2) n '- (L') m '- (OR) nO- (L ") m" -R '(II)
[0075] in which R 'is a hydrogen atom, an acyl group or an alkyl group, linear or branched, eventually substituted by one or more functional groups, which may also contain one or more double bonds, R being an alkylene group linear or branched, preferably linear, for example an ethylene or propylene group, L 'and L' 'are the divalent groups, X, Y and m are as defined below, n being an integer from 1 to 10, preferably from 1 to 5, n is an integer from 2 to 50, preferably from 5 to 30, more preferably from 5 to 15, m 'being equal to 0 or 1, preferably 0, m' 'being equal to 0 or 1 , preferably 0.
[0076] The groups L 'and L ", when present, can be selected from the divalent groups L previously described and preferably representing the group -OCH2CH (OH) CH2or the group -NHC (O) -. In this case, the OCH2CH (OH) CH2or -NHC (O) groups are linked to the adjacent groups (CH2) n '(in the case of an L' group) and R '(in the case of an L "group) via their oxygen atom (for the -OCH2CH (OH) CH2- group) or through its nitrogen atom intermediate (for the -NHC (O) - group).
[0077] The group -O- (L ") m — R 'is preferably an alkoxy group (m" = 0, R' = alkyl), ideally a methoxy group.
[0078] Preferably, the compounds of formula (I) or (II) comprise a single silicon atom carrying at least one hydrolyzable group.
[0079] According to an embodiment, m = 0 and the hydrolyzable groups X designate the methoxy or ethoxy groups, n 'is preferably equal to 3. According to another embodiment, R' designates an alkyl group having less of 5 carbon atoms, preferably the methyl group. R 'can also designate an aliphatic or aromatic acyl group, particularly the acetyl group.
[0080] Finally, R 'can designate a trialcoxysilylalkylene or trihalogenosylylalkylene group, such as the group - (CH2) n''Si (R5) 3 where R5 is a hydrolyzable group such as the groups X defined above and n' 'is an integer such as group n 'defined above. An example of such a group R 'is the (CH2) 3Si (OC2H5) 3 group. In accordance with this embodiment, the organosilane compound contains two silicon atoms with at least one hydrolyzable group.
[0081] According to the preferred embodiments, n is equal to 3 or can vary from 6 to 9, from 9 to 12, from 21 to 24, or from 25 to 30, preferably from 6 to 9.
[0082] Examples of compounds of formula II include 2 [methoxy (polyethyleneoxy) propyl] trimethoxysilane 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 = 2124, the 2- [methoxy (polyethyleneoxy) propyl] trichlorosilanes, the 2- [acetoxy (polyethyleneoxy) propyl] trimethoxysilane of the formula CH3C (O) O- (CH2CH2O) 6-9- (CH2) 3Si (OCH3) 3, o 2 [acetoxy (polyethyleneoxy) propyl] triethoxysilane of formula CH3C (O) O- (CH2CH2O) 6-9 (CH2) 3Si ( OC2H5) 3, the 2- [hydroxy (polyethyleneoxy) propyl] trimethoxysilane of the formula HO (CH2CH2O) 6-9- (CH2) 3Si (OCH3) 3, the 2- [hydroxy (polyethyleneoxy) propyl] triethoxysilane of the formula HO- ( CH2CH2O) 6-9- (CH2) 3Si (OC2H5) 3, the 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] oxide of formula (V), polyethylene-bis [(N, N'-triethoxysilylpropyl) -aminocarbonyl] oxide of formula (VI) with n = 10-15 and polyethylene-bis (triethoxysilylpropyl) oxide of formula (VII):

Preferred compounds of formula II are [alkoxy (polyalkyleneoxy) alkyl] trialcoxysilanes or their trihalogenated analogs (m = m '= m "= 0, R' = alkoxy).
[0084] Preferably, the organosilane compound of the invention does not have a fluorine atom. Typically, the weight ratio of fluorine in the precursor coating to the anti-fog coating is less than 5%, preferably less than 1% by weight and more preferably 0%.
[0085] Preferably, the molar mass of compound A according to the invention ranges 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 to 1000 g / mol.
[0086] According to an embodiment of the invention, the precursor of the anti-fog coating comprises more than 80% by weight of the organosilane compound according to the invention, in relation to the total mass of the precursor of the anti-fog coating, of preferably more than 90. According to an embodiment, the precursor of the anti-fog coating consists of a layer of said organosilane compound.
[0087] Preferably, the antifog coating precursor of the invention contains less than 5% by weight of metal oxide or metalloid (for example, silica or alumina) relative to the total mass of the coating, more preferably not understands. When the organosilane compound used to form an anti-fog coating is deposited under vacuum, preferably no metal oxide is co-evaporated with it, according to the co-evaporation technique of at least one organic compound and of at least one inorganic compound described in application EP 1324078.
[0088] The precursor of the anti-fog coating of the invention preferably has a static contact angle with water strictly greater than 10 ° and strictly less than 50 °, preferably less than or equal to 45 °, more preferably <40 °, even more preferably <30 ° and ideally <25 °. This contact angle is preferably from 15 ° to 40 °, more preferably from 20 ° to 30 °. Its surface energy is preferably at least 15 mJ / m2, more preferably at least 25 mJ / m2. These different values are verified by the precursor of the anti-fog coating initially deposited (including an excess of compound A) and / or the precursor of the anti-fog coating resulting from the elimination of the temporary layer of the invention, preferably by both.
[0089] The deposition of compound A on the surface of the coating containing silanol groups can be carried out according to the usual techniques, preferably by deposition in gas or liquid phase, ideally in gas phase, by evaporation under vacuum. Compound A can be previously dissolved in a solvent before being evaporated, to better control the rate of evaporation and deposition.
[0090] According to one of the embodiments of the invention, the precursor coating is deposited by applying a composition comprising a hydrolyzate of compound A, in which this is an organosilane. In that case, it is recommended to apply the composition quickly enough after hydrolysis, typically less than 2 hours, preferably less than 1 hour, more preferably less than 30 minutes after proceeding with hydrolysis (by adding an acidic aqueous solution, typically HCl) , to limit the formation of siloxane prepolymers before grafting. It is always preferred to deposit said organosilane by gas.
[0091] After depositing compound A in accordance with the invention, the external part of the wipe-eliminable coating is preferably not removed, either by washing or wiping, or it may be only partially. This precursor coating, therefore, presents problems of adhesion to the support block during the overhang.
[0092] At least one temporary layer according to the invention is formed directly on the precursor coating of the anti-fog coating. Several temporary layers according to the invention based on identical or different materials can be formed on top of each other.
[0093] According to an embodiment, the precursor coating of the anti-fog coating is coated by two temporary layers adhering to each other, identical or different, each temporary layer comprising at least 50% by mass of silica, in relation to the total mass of this temporary layer.
[0094] However, it is preferred to use a single temporary layer or two, ideally a single one. The present description is essentially written in this light with the concern to summarize, but it also applies to the case of the use of a plurality of temporary layers.
[0095] This layer comprises at least 50% by mass of silica, compared to the total mass of the temporary layer, preferably at least 60%, more preferably at least 70% by mass of silica. It preferably comprises at least 80%, more preferably at least 90% and even more preferably at least 95% by mass of silica. According to an embodiment of the invention, the temporary layer consists of a layer of silica.
[0096] When the temporary layer does not comprise only silica, it comprises other materials that are preferably dielectric materials such as metal oxides, preferably alumina (Al2O3).
[0097] When a temporary 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 compared to the total mass of SiO2 + Al2O3 in that layer. For example, SiO2 enriched with 2 to 4% Al2O3 by weight, or SiO2 enriched with 2.5 to 5% by weight, or SiO2 enriched with 4 to 8% by weight of Al2O3 can be employed. The commercially available SiO2 / Al2O3 mixtures can be used, such as LIMA® 4 or LIMA® 8 marketed by Umicore Materials AG, or the L5® substance marketed by Merck KGaA.
[0098] The material of the temporary layer according to the invention does not alter the surface properties of the precursor coating of the anti-fog coating and is liable to be eliminated during a subsequent operation subsequent to the finishing step. The material of this temporary layer also has a sufficient cohesive force so that the temporary layer is removed without leaving residues on the surface of the precursor coating of the anti-fog coating.
[0099] In general, the temporary layer must be thick enough to avoid any further alteration of the properties of the precursor coating of the anti-fog coating during the different treatment stages of the article. Its thickness is preferably> 5 nm, more preferably> 10 nm and preferably <200 nm, more preferably <100 nm and even more preferably <50 nm. It typically ranges from 5 to 200 nm, preferably from 10 to 100 nm.
[0100] The temporary layer preferably has a static contact angle with water less than 50 °, more preferably less than 40 ° and even more preferably less than 30 °. Its surface energy is preferably at least 15 mJ / m2, more preferably at least 25 mJ / m2.
[0101] The temporary layer can be deposited by any suitable classical process, in the vapor phase (vacuum deposition), or in the liquid phase, for example by spraying, centrifuging or immersion.
[0102] The temporary layer is preferably deposited via gas, particularly by evaporation under vacuum. In fact, vacuum treatment deposition allows precise control of the thickness of the temporary layer and minimizes dispersions, which is not necessarily the case with other available technical solutions. On the other hand, this vacuum treatment has the advantage that it can be directly integrated into the industrial process for treating optical articles, particularly when they are equipped with an anti-reflective coating.
[0103] Preferably, the deposition of the temporary layer is carried out in a vacuum enclosure with no additional gas entering during the deposition step. This deposition technique, which is preferable to avoid, called deposition under regulation of gas pressure, consists of introducing a supplementary gas called "passive" such as, without limitation, argon, oxygen or their mixtures, into the deposition enclosure under vacuum during the deposition of a layer. This deposition under pressure regulation is different from deposition under ionic assistance.
[0104] The temporary layer is formed so that it covers, at least partially, the precursor coating of the anti-fog coating.
[0105] The deposition can be carried out on the entire surface of the face of the optical article intended to receive the maintenance / adhesion support block system or on a part thereof. In particular, the temporary layer can only be applied over the area intended to receive the contact of the maintenance block, for example the central part of the article.
[0106] The temporary layer can uniformly cover the target surface, i.e., present a continuous structure, but it can also present a discontinuous structure, for example taking the form of a weft. This type of structure can be obtained by applying a mask to the surface of the article, in order to limit the deposition of the temporary layer in the desired zone.
[0107] The area covered by the temporary layer is such that the contact surface between that layer and the maintenance block is sufficient to ensure the adhesion of the lens to the block. Generally, the temporary layer covers at least 15%, preferably at least 20%, more preferably at least 30%, even more preferably at least 40% and preferably the entire surface of the face of the optical article on which the block adheres. , ie, in the case of a lens, its convex surface.
[0108] After depositing the temporary layer according to the invention, an optical article suitable for edging is obtained. This temporary layer preferably constitutes the outer layer of the optical article, i.e., the layer that is in contact with air. However, it is possible to deposit other films or temporary layers on it allowing the edging of the optical article, particularly a film of polymeric nature, formed for example from a latex, giving the article a surface energy preferably greater than or equal to 15 mJ / m2.
[0109] The temporary layer used in the present invention has several advantages. It does not affect the transparency of the optical article, so that it is possible to carry out the classical power measurements on a article coated with such a temporary layer by means of a front lens. It can be marked with various marking inks, commonly used by the person skilled in the art for progressive glass lenses. It thus has a mechanical resistance generally sufficient to withstand the friction generated during the storage and handling of the articles, particularly when the articles are ophthalmic lenses stored and distributed inside paper bags.
[0110] It is possible to deposit an electrostatic adhesive film on the surface of the temporary layer as described in patent application EP1664906.
[0111] The invention also relates to a process of edging an optical article as defined above, comprising: fixing the optical article to a maintenance device through an adhesive block adhering to the surface of the optical article (blocking) ; the assembly of the maintenance device to which the optical article adheres by means of an adhesive block in a beading device; the edging of the optical article by machining the periphery of the optical article; and after the recovery of the optical article (unlocking), the elimination of the temporary layer.
[0112] In the case where the optical article is a lens glass, the edging step allows it to be adjusted to the dimensions and shape of a frame.
[0113] The temporary layer, or overlayer, allows the support block to be applied directly to the optical article and keeps it firmly throughout the beading operation, on the one hand due to its good adhesion to the precursor coating of the anti- fogging and on the other hand in improving the normal and tangential adhesion of the block to the surface of the article. Thus, it avoids the phenomena of slipping and misalignment, as well as the phenomenon of unblocking and allows a reliable overhang.
[0114] On the other hand, it allows for very good maintenance of the article after over-cutting. After the main beading operation of the optical article, we may in fact wish to carry out a beading recovery operation, and / or a perforation, serving the perforated area for example as a fixation point with a branch of the glasses frame in the case of the glasses glasses. For these last steps, described particularly in the application WO 2009/071818, and in particular for the perforation of glass, it is essential that the adhesion set / adhesive maintenance block remains in position on the surface of the article, because it constitutes a reference point , allowing to position the drills to drill the holes.
[0115] The locking, unlocking and maintenance systems usable throughout this process, classic for the person skilled in the art, are described in more detail in EP 1392613 and WO 2010/055261.
[0116] The edging process according to the invention provides optical articles subject to a maximum misalignment of 2 ° and, optimally, less than or equal to 1 °.
[0117] The overlapping step can possibly be followed by an overlapping recovery step and / or a drilling step, before the temporary layer is eliminated.
[0118] The temporary layer according to the invention has the interest of being able to be eliminated very easily after the edging.
[0119] The step of removing this layer can be carried out either in a liquid medium, or by wiping, particularly dry, or by a combined procedure of these two means. This step can be selected from the washing and drying steps mentioned above. Other means of disposal in liquid medium are described, particularly in application WO 03/057641. Wiping with a cloth or cloth is the preferred disposal technique.
[0120] After removing the temporary layer, also resulting in the elimination of excess deposited compound A, ie, the outer part of the precursor coating of the anti-fog coating that can be wiped away does not remain on the surface of the coating containing silanol groups on its surface. otherwise, the inner part of the precursor coating of the anti-fog coating containing compound A effectively grafted. The non-grafted molecules are thus evacuated.
[0121] The thickness of the precursor coating of the anti-fog coating remaining after this elimination step is preferably less than or equal to 5 nm, more preferably less than or equal to 3 nm. Compound A deposited on the surface of the optical article therefore preferably forms a monomolecular or almost monomolecular layer.
[0122] This process may, on the other hand, comprise an additional step of deposition of a film of a liquid solution containing at least one surfactant on the surface of the precursor coating of the anti-fog coating obtained after the removal of the temporary layer and the outer part of the precursor coating of the anti-fog coating that can be wiped away, thus providing access to a temporary anti-fog coating.
[0123] An optical article is thus recovered having excellent anti-fog properties, which means that the temporary layer according to the invention does not have any negative influence on the anti-fog properties of the article. It no longer affects the durability of the properties of the anti-fog coating.
[0124] This solution provides glasses with temporary protection against fogging, by creating a uniform layer on their surface that helps to disperse the water droplets on the glass surface so that they do not form visible fogging.
[0125] The surfactant solution can be applied by any known technique, particularly by immersion, centrifugation or spraying.
[0126] The surfactant solution is preferably applied by depositing a drop of that solution on the surface of the precursor of the anti-fog coating, then spreading to preferably cover the entire said precursor coating.
[0127] The applied surfactant solution is generally an aqueous solution, preferably containing from 0.5 to 10%, more preferably from 2 to 8% by weight of surfactant.
[0128] A wide variety of surfactants can be employed. These can be ionic (cationic, anionic or amphoteric) or non-ionic, preferably non-ionic or anionic. However, a mixture of surfactants belonging to these different categories is possible. Preferably, a surfactant containing poly (oxyalkylene) groups is used.
[0129] Advantageously, a commercial maintenance solution containing a surfactant, available in the form of vaporizer or wipes. A surfactant solution available on the market to provide anti-fog properties is the Clarity Defog it® solution from Nanofilm.
[0130] 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 °.
[0131] The invention also relates to a process for preparing an optical article, preferably an ophthalmic lens, as defined above, comprising: a) providing a substrate on which at least one of the main surfaces is coated with a coating containing silanol groups on its surface, b) deposition on said coating, preferably by vacuum evaporation, of at least one compound A having a polyoxyalkylene group and at least one group capable of establishing a covalent bond with a silanol group, in order to obtain a precursor coating of an anti-fog coating comprising an internal part in which said compound A is grafted into the coating containing silanol groups on its surface, and an external part which can be removed by washing and / or wiping, c ) deposition on the precursor coating of the anti-fog coating, preferably by evaporation under vacuum, at least a temporary layer comprising at least minus 50% by mass of silica, compared to the total mass of the temporary layer.
[0132] The following examples illustrate the invention in a more detailed but not limiting way. Unless otherwise stated, all thicknesses included in the scope of this application are measured physical thicknesses. EXAMPLES 1. Materials and optical articles used
[0133] Silica is used in the form of granules supplied by Optron Inc. The mixtures of silica and alumina were supplied by Umicore and Merck KGaA. The organosilane compound used in the examples to form the precursor to the anti-fog coating is 2 [methoxy (polyethyleneoxy) propyl] trimethoxysilane having 6 to 9 ethylene oxide units (examples 1-4, 6, 7), of formula (III ) and molar mass 450-600 g / mol (CAS No.: 65994-07-2, Ref: SIM6492.7, supplied by Gelest, Inc.).
[0134] The vacuum evaporation device allowing the deposition of different layers (antireflection, precursor coating of the anti-fog coating, temporary layer) is a SATIS 1200 DLF machine (starting pressure, in which the process will start: 3.5.10-3 Pa ).
[0135] The glasses used in the examples according to the invention comprise a bisphenol A polycarbonate lens substrate (correction -8.00 diopters, +2.00 cylinders), containing on each face a primary anti-shock layer of a thickness of the order of 1 micron, itself coated with an anti-abrasion coating of a thickness of the order of 3 microns in deposition and hardening of a composition as defined in example 3 of application EP 614957, coated in turn with a coating anti-reflective coating with five layers ZrO2 / SiO2 / ZrO2 / ITO / SiO2 deposited on the anti-abrasion coating by vacuum evaporation of the materials in the order in which they were mentioned (respective layer thicknesses: 29, 23, 68, 6.5 and 85 nm , respective deposition speeds: 0.32, 0.7, 0.32, 0.13, 1.05 nm / s). The ZrO2 layers are deposited with the introduction of passive O2 (6.10-3 Pa) without ionic assistance. The ITO layer is deposited under the ionic assistance of oxygen ions (2 A, 120 V) without the contribution of passive O2. An ITO layer is an electrically conductive layer of tin-enriched indium oxide (In2O3: Sn).
[0136] Before the deposition of the anti-reflective coating, the glasses containing the anti-abrasion coating are subjected to a surface activation treatment (IPC) which consists of an ion bombardment with argon ions, under vacuum, at a pressure of typically 3.5.10-5 mbar (1 minute, 3 A, 150 V).
[0137] In the examples, the anti-reflective coating is not subjected to any activation treatment before deposition of the precursor of the anti-fog coating. 2. Deposition of the precursor of the anti-fog coating in the vapor phase
[0138] The deposition is carried out on the anti-reflective coating of the lenses by evaporation under vacuum using a thermal source by Joule effect. 150 μL of siloxane compound of formula (III) are poured into a copper capsule, and that capsule is deposited on a heated, conductive tantalum support. The evaporation pressure of the siloxane compound of formula (III) generally ranges from 5.10-4 to 8.104 Pa (deposition rate: 0.3 nm / s). A layer of 9 to 15 nm in thickness is obtained according to the tests (including excess siloxane compound), having a static contact angle with water of 13 °. 3. Deposition of temporary layers
[0139] Temporary layers, according to the invention or comparative, of 7, 12, 24 or 48 nm in thickness were formed on the precursor coatings of the anti-fog coatings described above by vacuum evaporation in a vacuum atmosphere room (speed of deposition: 0.7 nm / s) P = 3.10-3 Pa, without supply of passive gas or ionic assistance. Ophthalmic lenses are obtained with a generally bluish appearance (which disappears after wiping and / or washing). Other colors are possible according to the thickness and refractive index of the temporary layer. The temporary layers according to the invention having static contact angles with water from 22 to 23 °.
[0140] The performances of the articles thus prepared were evaluated and subjected to four tests described in the following paragraph, one week after their preparation. 4. Performance evaluation of prepared articles a) Unlock test
[0141] The unlocking test consists of gluing an adherent set + support block on the convex face of a glass, then subjecting the set to a sprinkling of tap water (water at 25 ° C) for 45 seconds, in order to reproduce the exposure to water fluently used during the overrun. The behavior of the adherent set + support block on the glass throughout the test is observed. The rating system is as follows: 0 = poor support block behavior 1 = good support block behavior, the support block is easy to remove 2 = good support block behavior, the support block is difficult to remove b) Test of elimination of the temporary layer by wiping
[0142] The temporary layer is dried manually with the aid of a SelvithTM type cloth in order to remove and obtain the glasses containing an outer layer with a precursor coating of the anti-fog coating. The rating system is as follows: 0 = temporary layer impossible to remove with a dry or damp cloth 1 = temporary layer difficult to remove with a dry or damp cloth 2 = temporary layer easy to remove with a dry cloth c) Anti-fog performance test
[0143] The glasses subject to this test were previously submitted to the temporary layer elimination test described in § b). The Clarity® Defog It solution was subsequently applied to the surface of these glasses only once, containing the surfactants (polyethylene glycols, in isopropanol solution), marketed by the company Nanofilm.
[0144] The glasses were subsequently placed 24 hours in an environment regulated by temperature (20-25 ° C) and 50% humidity.
[0145] The glasses were then placed for 15 seconds over a heated container containing water at 55 ° C. Immediately thereafter, a visual acuity scale located at 5 m is observed through the tested glass. The observer assesses visual acuity (in transmission) according to the following criteria: 2 = No fogging, no visual distortion (visual acuity = 10/10 °) 1 = Visual fogging and / or distortion allowing visual acuity> 6/10 ° 0 = Blurring and / or visual distortion allowing visual care <6/10 °
[0146] Concretely, to obtain a score of 0 or 1, a bearer with a vision of 10/10 and with the glass placed before his eyes must be able to distinguish the orientation of the letters "E" on line 6/10 of Snellen's Optotype table placed at 5 meters (ECHELLE ARMAIGNAC Tridents, ref. T6 available at FAX INTERNATIONAL).
[0147] This test allows you to simulate the day-to-day living conditions in which the wearer places his face over his tea, coffee or a pot of boiling water. d) Edging test
[0148] The edging test, performed on an Essilor Kappa grinder, as well as the misalignment measurement protocol suffered by the lenses during this operation, are described in detail in the application WO 2009/071818. In the course of this test, the adhesive support block employed (LEAP II of diameter 24 mm GAM200 of the company 3M) is directly in contact with the temporary layer. A lens is considered to pass the edging test if it is misaligned by 2 ° or less. 5. Results a) Study of the influence of the nature of the materials that make up the temporary layer.
[0149] Table 1 demonstrates that the temporary layers according to the invention, i.e., based on silica or a mixture of silica and alumina within the limit of 8% by mass, lead to satisfactory results. The lenses of examples 1-4 have a temporary layer allowing the rim to be carried out in good conditions, which can be easily removed and which, after removing a certain layer, provides a lens having the expected anti-fog performance.
[0150] The results are satisfactory, the temporary silica layer is evaporated or not with passive oxygen input during evaporation.
[0151] It has also been found that materials such as alumina or tin oxide, when used pure, as a temporary layer, interfere with the anti-fog performance of the glass, which can be explained by contamination or extraction of the precursor of the anti-fog coating during the removal of the temporary layer. Alumina, on the other hand, is a temporary layer that is difficult to remove. It should be noted that the poor results obtained for some glasses in the anti-fog performance test can be explained by the fact that the temporary layer has not been completely eliminated.
[0152] Other layers that are not suitable for use as a temporary layer according to the invention are the layers consisting of chromium, ITO and TiO2.
[0153] The thickness of the temporary layer is a parameter with limited influence. In either case, it appears that increasing the thickness of the temporary layer slightly decreases the anti-fog, elimination or unblocking classification. The nature of the material that forms the temporary layer is the most important parameter.Table 1 (thickness of the precursor coating of the anti-fog coating: 12nm)
(*): Supply of oxygen during the deposition of the temporary layer, generating a porous layer. (**): Lima® 8 from Umicore, containing from 4 to 8% by weight of alumina. (***): L5® from Merck KGaA, containing from 2.5 to 5% by weight of alumina.
[0154] It was found that the performance in terms of unlocking, eliminating and the blurring performances of the lenses of Examples 1 to 4 were maintained at least one month after preparation. To work in optimal conditions, it is recommended to trim the lenses that have a temporary layer according to the invention, within a month. In addition to an excessively long period of time, the temporary layer according to the invention becomes slightly more difficult to remove without, however, leading to a lower performance in the tests of unlocking and evaluation of anti-fog performance.
[0155] It was also found that the evaporation rate of the precursor material of the temporary layer had little influence on the performance of the prepared lenses.
[0156] It should be noted that, after removing the temporary layer, the precursor coating of the anti-fog coating has a static contact angle with water of the order of 35-37 ° (Examples 1-4).
[0157] Regarding the edging test (performed on the lenses containing a precursor of the 12 nm thick anti-fog coating and a temporary layer of SiO2 / Al2O3 L5® of 7 nm thickness), the lenses according to the invention do not suffered any deviation. Adherents hardly detach from the adhesive, remaining glued to the convex surface of the glass. Considering the good behavior of the support block, these lenses are capable of undergoing a bead or perforation recovery operation. It was found that the lenses that do not contain any temporary layer failed the edging test. b) Study of the influence of the thickness of the precursor coating of the anti-fog coating
[0158] Table 2 shows that changing the thickness of the precursor anti-fog coating can allow modulating the performances of the optical article. Thus, an increase in the thickness of the precursor coating of the anti-fog coating improves the ease of removal of the temporary layer and improves the anti-fog performance, but reduces the overhang capacity.
[0159] However, the nature of the material that forms the temporary layer is the most important parameter.
[0160] Therefore, it is possible to optimize the thickness of the temporary layer comprising, according to the invention, at least 50% by mass of silica, and the thickness of the precursor of the anti-fog coating deposited in excess, in order to achieve simultaneously achieve a product that borders in total safety, with a good anti-fog performance and whose temporary overlapping layer is easy to eliminate.Table 2
(***): Substance L5® from Merck KGaA, containing from 2.5 to 5% by weight of alumina. c) Study of the influence of the overlap of the two temporary layers according to the invention
[0161] Table 3 demonstrates that it is possible to stack two temporary layers according to the invention, whose thicknesses are not optimized, to produce a temporary bi-layer leading to satisfactory results in the three tests performed. Table 3 (thickness of the precursor coating of the anti coating - fog: 12nm)

(***): Substance L5® from Merck KGaA, containing from 2.5 to 5% by weight of alumina.

权利要求:
Claims (16)
[0001]
1. Optical article comprising a substrate in which at least one of the main surfaces is coated with a first coating having silanol groups on its surface and, in direct contact with this coating, a second coating, precursor to an anti-fog coating, the second coating being formed by deposition on the first coating of at least one compound A having: a polyoxyalkylene group, and at least one group capable of establishing a covalent bond with a silanol group, characterized in that the second coating comprises an inner portion in which said compound A is grafted onto the first coating, and an outer portion which can be eliminated by washing and / or wiping, resulting from the deposition of compound A, and wherein the second coating is coated with at least one temporary layer, comprising at least 50% in mass of silica, in relation to the total mass of the temporary layer.
[0002]
2. Optical article according to claim 1, characterized in that the temporary layer is the outermost layer of the optical article, in contact with air.
[0003]
Optical article according to claim 1 or 2, characterized in that the precursor coating of the anti-fog coating has a thickness of 3 and 100 nm.
[0004]
Optical article according to any one of claims 1 to 3, characterized in that compound A is an organosilane, the group being able to establish a covalent bond with a silanol group a silicon atom carrying at least one hydrolyzable group.
[0005]
5. Optical article according to claim 4, characterized in that the organosilane compound is a compound of the formula: R1YmSi (X) 3-m (I) in which the Y groups, identical or different, are monovalent organic groups linked to the silicon by a carbon atom, groups X, identical or different, are hydrolyzable groups or hydroxyl groups, R1 is a group comprising a polyoxyalkylene function, m is an integer equal to 0, 1 or 2.
[0006]
Optical article according to any one of claims 1 to 5, characterized in that the temporary layer comprises 1 to 10%, by weight of alumina in relation to the total mass of the temporary layer.
[0007]
Optical article according to any one of claims 1 to 5, characterized in that the temporary layer consists of a layer of silica.
[0008]
Optical article according to any one of claims 1 to 7, characterized in that the temporary layer has a thickness of 5 to 200 nm.
[0009]
Optical article according to any one of claims 1 to 8, characterized in that the precursor coating of the anti-fog coating has a surface energy greater than or equal to 15 mJ / m2.
[0010]
Optical article according to any one of claims 1 to 9, characterized in that the coating containing silanol groups on its surface is an anti-reflective coating or a silica-based layer deposited on an anti-abrasion coating.
[0011]
11. Optical article according to any one of claims 1 to 10, characterized in that it is an optical lens.
[0012]
Optical article according to any one of claims 1 to 11, characterized in that the second coating is coated with a single temporary layer comprising at least 50% by mass of silica, in relation to the total mass of the temporary layer.
[0013]
Optical article according to any one of claims 1 to 12, characterized in that the second coating is coated with two temporary layers adhering to each other, identical or different, each temporary layer comprising at least 50% by mass of silica, in relation to the total mass of this temporary layer.
[0014]
14. Beading process of an optical article as defined in any of claims 1 to 13, characterized in that it comprises: the attachment of the optical article to a maintenance device through an adhesive block adhering to the surface of the optical article; the assembly of the maintenance device to which the optical article adheres by means of an adhesive block in a beading device; the edging of the optical article by machining the periphery of the optical article; and after recovery of the optical article, the elimination of the temporary layer.
[0015]
Process according to claim 14, characterized in that the thickness of the precursor coating of the anti-fog coating after removal of the temporary layer is less than or equal to 5 nm.
[0016]
16. Process for preparing an optical article as defined in any one of claims 1 to 13, characterized in that it comprises: a) providing a substrate in which at least one of the main surfaces is coated with a first coating containing in the its surface silanol groups, b) deposition on said first coating of at least one compound A having a polyoxyalkylene group and at least one group capable of establishing a covalent bond with a silanol group, in order to obtain a second coating, precursor of an anti-fog coating, comprising an inner part in which said compound A is grafted into the first coating and an external part removable by washing and / or wiping, c) deposition on the second coating, precursor of the anti-fog coating by less than a temporary layer comprising at least 50% by mass of silica, based on the total mass of the temporary layer.

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同族专利:

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公开号 | 公开日

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US20150062704A1|2015-03-05|

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BR112013029191A2|2017-01-31|

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CN103518147B|2016-03-23|

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WO2012153072A1|2012-11-15|

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EP2707762B1|2015-10-21|

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JP2014514615A|2014-06-19|

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EA201301249A1|2014-03-31|

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EA024639B1|2016-10-31|

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US9435914B2|2016-09-06|

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EP2707762A1|2014-03-19|

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CA2835801A1|2012-11-15|

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法律状态:
2018-07-31| B25A| Requested transfer of rights approved|Owner name: ESSILOR INTERNATIONAL (FR) |

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

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2020-01-14| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-10-20| B09A| Decision: intention to grant|

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2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/05/2012, 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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FR1154128|2011-05-12|

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FR1154128|2011-05-12|

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PCT/FR2012/051044|WO2012153072A1|2011-05-12|2012-05-11|Optical article comprising a precursor coating for an antifogging coating and a temporary layer rendering same suitable for edging|

---