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    • 专利摘要:
    The present invention relates to an optical article having a substrate coated with a precursor coating of an anti-fog coating whose surface has a static contact angle with water greater than 90 ° and a polar surface energy component. greater than 1.5 mJ / m2. The anti-fogging precursor, which furthermore has anti-fouling properties, is converted into an anti-fogging coating itself by applying a film of surfactant to its surface.
    公开号:FR3014210A1
    申请号:FR1362048
    申请日:2013-12-03
    公开日:2015-06-05
    发明作者:Mamonjy Cadet；Alexis Theoden
    申请人:Satisloh AG；
    IPC主号:
    专利说明:

    [0001] The present invention is concerned with obtaining an optical article, more particularly an ophthalmic lens, the surface of which has been modified so as to have both anti-fouling properties and to exhibit an effective and lasting anti-fogging effect. in time after application of a temporary anti-fog solution. The present invention relates to such an article, its method of preparation and its combination with a surfactant or a fabric impregnated with such a surfactant conferring anti-fogging properties. Many substrates, such as plastics and glass, have the disadvantage of fogging up when the temperature of their surface falls below the dew point of the ambient air. This is particularly the case of glass used to form glazing for transport vehicles or the building, mirrors, ophthalmic lenses such as spectacle lenses, etc. The formation of mist on these surfaces causes a decrease in transparency, due to the diffusion of light by the drops of water, which can cause significant discomfort. To avoid the formation of mist in a very humid environment, that is to say the condensation of tiny water droplets on a support, it is possible to deposit on the outer surface of this support hydrophilic coatings having a low static contact angle with water (typically 10 ° or less). These permanent anti-fog coatings, whose hydrophilic properties are derived from hydrophilic compounds permanently bonded to another coating or support, act as sponges to the mist and allow the water droplets to adhere to the surface of the surface. support by forming a very thin film giving a feeling of transparency. As a result of the absorption of water, they swell, soften and become less mechanically resistant. Another solution is to use a porous thin layer of low refractive index, consisting in part of surfactants, which allow the layer to acquire permanent anti-fogging properties. A more interesting alternative to permanent anti-fogging coatings is to obtain an anti-fog coating by applying a temporary hydrophilic solution to the surface of a precursor coating of an anti-fog coating. It has been described in international patent applications WO 2011/080472, WO 2012/153072 and WO 2013/013929 the deposition, on the outer surface of an optical article coated with a coating comprising on its surface silanol groups. , a precursor coating of an anti-fogging coating obtained by grafting a compound having a polyoxyalkylene group, in particular an organosilane of formula CH 3 O- (CH 2 CH 2 O) 6 -9- (CH 2) 3 Si (OCH 3) 3 (III). This precursor coating of an anti-fog coating is hydrophilic since it has a static contact angle with water ranging from 10 ° to 50 °. The actual anti-fogging coating, which is a temporary coating, is obtained after applying a film of a surfactant composition to the surface of the precursor coating, directly in liquid form or by means of dry or wet wipes comprising said composition.
    [0002] The anti-fog precursors described in these applications provide access to high performance anti-fog coatings, but for which it is desirable to improve the cleanability. The latter, also called "hydrophobic and / or oleophobic coatings", are generally manufactured from fluorosilanes or fluorosilazanes, that is to say silanes or silazanes containing fluorine atoms, and do not naturally allow to confer anti-fogging properties. Compounds useful for obtaining such antifouling coatings are disclosed in JP 2005187936 and US 6183872. Japanese Application JP 2004/317539 discloses a lens coated with an antireflection coating and a coating formed by depositing a compound comprising a fluorinated hydrophobic group, a hydrophilic group comprising a polyoxyethylene group and a group capable of reacting with the surface of the substrate, for example the compound of formula C8F170 (CH2CH2O) 2CONH (CH2) 3Si (OCH3) 3. The coating thus formed has an angle of contact with water ranging from 50 to 90 ° and gives access to an anti-fog coating after application to its surface of a surfactant.
    [0003] Japanese application JP 2005/281143 discloses other optical lens coatings based on nonfluorinated silanes having polyoxyethylene groups having water contact angles of the order of 60-65 °, which once an applied surfactant has been applied. on their surface, have anti-fogging properties. International Application WO 2006/049020 discloses a composition for forming on the surface of an optical lens an antifouling coating, comprising a fluorinated polymerizable silane and a polymerizable silane having a hydrophilic group (especially an oxyalkylene group), and / or hydrolysates of these silanes. These coatings have angles of contact with water of the order of 100 °. International application WO 2013/005710 discloses an optical article successively coated with a layer capable of absorbing water based on an acrylic resin or urethane having a polyoxyethylene chain and a hydrophobic layer based on a aminomodified silane or mercapto-modified silane. The outer surface of the article thus has an angle of contact with the water greater than or equal to 100 °. The coatings disclosed in these various applications have either antifouling properties that can be improved, or insufficient anti-fogging properties that can be improved. The present invention aims to obtain an optical article comprising an anti-fog coating precursor coating, whose anti-fouling properties would be improved over known precursor coatings. The inventors have discovered that the use of "mixed" surfaces, having both hydrophilic functions and hydrophobic functions, made it possible to maintain a satisfactory anti-fogging performance while significantly improving the ability of the coating to be cleaned.
    [0004] The objectives of the invention are achieved by an optical article having a substrate coated with a precursor coating of an anti-fog coating whose surface has a static contact angle with water greater than 90 ° and a polar component surface energy greater than 1.5 mJ / m2.
    [0005] The invention further relates to a method for preparing such an optical article, comprising: a) providing a substrate having at least one major surface, b) depositing on said main surface of the substrate at least one hydrophilic compound A and at least one minus a hydrophobic compound B, so as to obtain a precursor coating for an anti-fog coating whose surface has a static contact angle with the water greater than 90 ° and a polar component of the surface energy greater than 1.5 mJ / m2. The invention further relates to an assembly comprising the optical article as defined above and a surfactant. The present invention will be described in more detail with reference to FIGS. 1 to 3 which show the dirt removal kinetics of an optical article according to the invention in comparison with optical articles of the prior art, under the effect of successive cleansing cycles. In the present application, a coating which is "on" a substrate / coating or which has been "deposited" on a substrate / coating is defined as a coating which (i) is positioned above the substrate / coating, (ii) not necessarily in contact with the substrate / coating, i.e. one or more intermediate coatings may be provided between the substrate / coating and the coating in question (however, it is preferably 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 will be understood that the layer 2 is further away from the substrate than the layer 1. Likewise, a so-called "outer" layer is further away from the substrate than a so-called "internal" layer. . By "anti-fog coating" is meant in the present application a coating which, when a transparent glass substrate coated with this coating is placed under conditions generating fogging on said substrate not equipped with said coating, allows immediate visual acuity> 6 / 10th "for an observer observing through the glass coated a scale of visual acuity located at 5 meters distance.A test to evaluate the anti-fogging properties of a coating is described in the experimental part. fogging, the anti-fog coatings may either not show fog on their surface (no visual distortion in the ideal case, or visual distortion but visual acuity> 6 / 10th "under the measurement conditions indicated above), or present fog on their surface but still allow, despite the disruption of vision caused by the mist, a visual acuity> 6/1 O th under the measurement conditions indicated above. A non-anti-fog coating does not allow visual acuity> 6/1 Oae as long as it is exposed to fogging conditions and generally has a condensation fog under the measurement conditions indicated above. By "anti-fogging glass" is meant in the present application a glass equipped with an "anti-fog coating" as defined above.
    [0006] By "precursor of an anti-fog coating" is meant in the present application a coating which, by application to its surface of a composition containing a surfactant so as to form a film, constitutes an anti-fog coating within the meaning of the invention. The composition comprising a surfactant can be a liquid solution applied directly to an optical article, ie a composition impregnating a wipe, this wipe being able to be wet or dry (absence of solvents), for example a CEMOITM dry wipe impregnated with Capstone TM FS3100 as described in patent application WO2013013929. The surfactants for forming an anti-fog film preferably comprise a fluorocarbon group and at least one polyoxyalkylene unit. The assembly consisting of the precursor coating and the surfactant-based solution film constitutes the anti-fog coating itself. Thus, the precursor of the anti-fog coating according to the invention, which is a coating having a hydrophobic surface, is not considered to be an anti-fog coating within the meaning of the invention. Indeed, this precursor anti-fog coating does not allow a visual acuity> 6 / 10th "under the measurement conditions indicated above.
    [0007] By temporary anti-fog coating means an anti-fogging coating obtained after the application of a liquid solution containing at least one agent conferring anti-fogging properties, preferably a surfactant, on the surface of a precursor coating of said anti-fog coating. The durability of a temporary anti-fog coating is generally limited by wiping its surface, the surfactant molecules not being permanently attached to the surface of the coating but simply adsorbed more or less sustainably. The optical article prepared according to the invention comprises a substrate, preferably transparent (Tg greater than 85%, better than 90%, better still greater than 95% and optimally greater than 97%. international standard definition (IS013666: 1998 and measured in accordance with IS08980-3), defined in the wavelength range of 380 to 780 nm), having front and rear main faces, one at least said main faces, preferably the two main faces, comprising at least one precursor coating of an anti-fog coating. By rear face (generally concave) of the substrate is meant the face which, when using the article, is closest to the eye of the wearer. Conversely, the front face (generally convex) of the substrate means the face which, when using the article, is furthest from the eye of the wearer.
    [0008] Although the article according to the invention may be any optical article likely to be confronted with a formation of mist, such as a screen, a glazing for the automotive industry or building, or a mirror, it is preferably an optical lens, more preferably an ophthalmic lens, for spectacles, or an optical or ophthalmic lens blank. This excludes items such as intraocular lenses in contact with living tissues or contact lenses, which are not intrinsically confronted with the problem of fogging. The precursor coating of the anti-fog coating is in direct contact with either a major surface of the substrate or a first coating when said major surface of the substrate is coated with a first coating. The first coating of the invention, which preferably has on its surface silanol groups, can be formed on at least one of the main faces of a bare substrate, that is to say uncoated, or on least one of the main faces of a substrate already coated with one or more functional coatings. In the rest of the application, the preparation of the layers will be described by direct deposition thereof on the optical article.
    [0009] The invention also comprises an embodiment in which the deposition of all or some of the layers is carried out on a film having a face comprising said coatings and a face intended to be adhered to the surface of the aticle. 'optical. In addition to gluing, the desired coatings can also be transferred to a support in which the coatings have been deposited in the opposite direction of the order in which they can appear on the final article. The substrate of the optical article according to the invention, which comprises at least one main surface, may be an inorganic or organic glass, for example an organic glass of thermoplastic or thermosetting plastic material.
    [0010] Particularly preferred classes of substrates are poly (thiourethanes), polyepisulfides and resins resulting from the polymerization or (co) polymerization of alkylene glycol bisalkylcarbonates. These are sold, for example, under the trade name CR-39® by PPG Industries (ORMA® ESSILOR lenses). Other substrates that can be used in the context of the invention are thermoset-type acrylic substrates, thermoplastic substrates such as Nylon ™ substrates, polycarbonate and PMMA. In some applications, it is preferable that the main surface of the substrate is coated with one or more functional coatings prior to deposition of the first coating. These functional coatings conventionally used in optics may be, without limitation, a layer of shockproof primer, an anti-abrasion and / or anti-scratch coating, a polarized coating, a photochromic coating or a colored coating, in particular a layer of shockproof primer coated with an anti-abrasion and / or anti-scratch layer.
    [0011] The first coating can be deposited on an anti-abrasion and / or anti-scratch coating. The anti-abrasion and / or anti-scratch coating may be any layer conventionally used as an anti-abrasion and / or anti-scratch coating in the field of ophthalmic lenses.
    [0012] The abrasion-resistant and / or scratch-resistant coatings are preferably hard coatings based on poly (meth) acrylates or silanes, generally comprising one or more mineral fillers intended to increase the hardness and / or the refractive index of the product. coating once cured. They are described in more detail in the application WO 2011/080472. Prior to the deposition of the anti-abrasion and / or anti-scratch coating, it is possible to deposit on the substrate a primer coating improving the impact resistance and / or the adhesion of the subsequent layers in the final product. These coatings may be any layer of impact-resistant primer conventionally used for articles made of transparent polymer material, such as ophthalmic lenses, and are described in more detail in the application WO 2011/080472.
    [0013] The first coating according to the invention may in particular be an anti-abrasion and / or anti-scratch coating, or, according to the preferred embodiment, a monolayer antireflection coating or a multilayer antireflection coating. This first coating preferably has on its surface silanol groups. By coating comprising on its surface silanol groups is meant a coating which naturally has on its surface silanol groups, or a coating whose silanol groups have been created after it has been subjected to surface activation treatment. . This coating is preferably a coating based on siloxanes or silica, for example, without limitation, a silica layer, a sol-gel coating, based in particular on organosilanes such as alkoxysilanes, or a coating based on colloids. of silica. It may be in particular an anti-abrasion and / or anti-scratch coating, or a monolayer antireflection coating or a multilayer antireflection coating whose outer layer has on its surface silanol groups. By outer layer of a stack is meant the layer furthest from the substrate. The surface-activating treatment optionally employed to create silanol groups or at least increase their proportion to the surface of a coating is generally conducted under vacuum. It can be a bombardment with energy and / or reactive species, for example an ion beam ("Ion Pre-Cleaning" or "IPC") or an electron beam, a discharge treatment corona, by effluvage, UV treatment, or vacuum plasma treatment. It can also be an acidic or basic surface treatment and / or by solvents. Many of these treatments can be combined. By energetic species (and / or reactive) is meant in particular ionic species having an energy ranging from 1 to 300 eV, preferably from 1 to 150 eV, better from 10 to 150 eV, and more preferably from 40 to 150 eV. The energetic species can be chemical species such as ions, radicals, or species such as photons or electrons. The coating comprising on its surface silanol groups is preferably a low refractive index layer based on silicon oxide, preferably silica (comprising silica), ideally consisting of a silica (SiO 2) layer, generally obtained by vapor deposition. Said silica-based layer preferably has a thickness less than or equal to 500 nm, better still from 2 to 110 nm, preferably ranging from 5 to 100 nm. The coating having on its surface silanol groups preferably comprises at least 70% by weight of SiO 2, more preferably at least 80% by weight and more preferably at least 90% by weight of SiO 2. As has been said, in an optimal embodiment, it comprises 100% by weight of silica. The coating having on its surface silanol groups may also be a sol-gel coating based on silanes such as alkoxysilanes, or organosilanes, and optionally comprising colloidal oxides, as described in more detail in WO 2012 / 153072. According to one embodiment of the invention, the coating comprising on its surface silanol groups is a silica-based layer deposited on an anti-abrasion coating, preferably deposited directly on this anti-abrasion coating. According to another embodiment of the invention, which constitutes the preferred embodiment, the optical article according to the invention comprises an antireflection coating. When such a coating is present, it is generally the first coating within the meaning of the invention. This antireflection coating may be any antireflection coating conventionally used in the field of optics, in particular ophthalmic optics. An antireflective 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 reduces the reflection of light at the article / air interface over a relatively large portion of the visible spectrum. As is also well known, antireflection coatings typically comprise a monolayer or multilayer stack of dielectric materials. These are preferably multilayer coatings, including high refractive index (HI) layers and low refractive index (BI) layers. The constitution of these coatings, their thickness and their mode of deposition are described in particular in applications WO 2010/109154 and WO 2012/153072. Prior to the formation of the precursor of the anti-fog coating on the first coating or on the bare substrate, it is common practice to subject the surface of this first coating or substrate to a physical or chemical activation treatment, intended to increase the adhesion of the coating. precursor of the anti-fog coating. These treatments may be chosen from those described above for the activation of the coating comprising on its surface silanol groups. According to the invention, the first coating, when present, is in direct contact with the precursor coating of the anti-fog coating. According to another embodiment, the substrate is itself directly in contact with the precursor coating of the anti-fog coating, which will now be described. The precursor coating of the anti-fog coating has a surface having a static contact angle with the water greater than 90 ° and a polar component of the surface energy greater than 1.5 mJ / m2.
    [0014] The surface energy characteristics (in mJ / m2), dispersive component and polar component of this surface energy are determined by the method of OWENS WENDT described in the reference: "Estimation of the surface force energy of polymers" OWENS DK , WENDT RG (1969) J. APPL-POLYM-SCI, 13, 1741-1747. It is considered that the surface energy, ET, for a liquid or a solid is composed of a dispersive component, ED, and a polar component, EP. It is written as ET = ED + EP. The outer coating of the optical article has a polar surface energy component which is preferably greater than or equal to 1.7 mJ / m 2, more preferably greater than or equal to 1.9 mJ / m 2, more preferably greater than or equal to 2 mJ / m 2 and more preferably greater than or equal to 2.3 mJ / m 2. It preferably has a static contact angle with water greater than or equal to 95 °, more preferably greater than or equal to 100 °, better than or equal to 102 °, and ideally greater than or equal to 105 °. static contact with water is preferably less than 120 °. The precursor coating of the anti-fog coating is generally formed of a material containing fluorocarbon groups and polyoxyalkylene groups, i.e. it comprises both hydrophilic units and hydrophobic units. According to a preferred embodiment, the precursor coating of the anti-fog coating is formed by depositing in sufficient quantities on the first coating or on the substrate at least one hydrophobic compound B, at least one hydrophilic compound A and preferably in phase gaseous, better by evaporation, followed by grafting. Compounds A and B are film-forming compounds. By hydrophilic compound is meant a compound of which a film formed on the surface of a substrate has a static contact angle with water of less than or equal to 60 °, preferably less than or equal to 55 °, better still less than or equal to 50 ° C. °. In this application, the contact angles are measured as described in WO 2008/053020.
    [0015] "Hydrophobic compound" means a compound of which a film formed on the surface of a substrate has a static contact angle with water greater than or equal to 75 °, preferably greater than or equal to 90 °, more preferably greater than or equal to equal to 100 °, better than or equal to 110 °. Preferably, the film known on the surface of a substrate has a static contact angle with water of less than or equal to 117 °, more preferably less than or equal to 116 °, 115 °, 114 °, 113 °. The hydrophilic compound A carries at least one hydrophilic group. By "hydrophilic" groups is meant, in the context of the present invention, combinations of atoms which are capable of associating with water molecules, in particular by hydrogen bonding. These are usually polar organic groups, which can include charged atoms. Compound A preferably comprises at least one group chosen from polyoxyalkylene, polyamine, polyol (polyhydroxyl group, for example a polysaccharide or polyglycerol group), polyether group (for example a polyol ether), and preferably a polyoxyalkylene group. Compound A generally comprises at least one group capable of establishing a covalent bond with a functional group present on the external surface of the substrate or of the first coating on which it will be grafted, or present in compound B, said functional group being preferably a silanol group in the case where a first coating is present. This group, which is a reactive group, may be, without limitation, one of the following groups: an isocyanate, acrylate, methacrylate, halogenoalkyl, carboxylic or sulfonic acid, phosphonic acid or ester, acyl chloride, chlorosulfonyl, chloroformate group , an ester, a silicon atom bearing at least one hydrolyzable group, or a group containing an epoxy functional group such as the glycidyl group, preferably a silicon atom bearing at least one hydrolyzable group, in particular a silanol group or a precursor of that -this.
    [0016] Compound A is preferably an organosilane compound, more preferably an organosilane compound having at least one silicon atom carrying at least one hydrolyzable group, more preferably an organosilane compound having a polyoxyalkylene group and at least one silicon atom bearing from least one hydrolysable group. Preferably, its polyoxyalkylene chain is functionalized at one end or at both ends, ideally at a single end, with at least one, preferably one, group comprising at least one silicon atom carrying at least one hydrolysable group. . This organosilane compound preferably comprises a silicon atom bearing at least two hydrolyzable groups, preferably three hydrolyzable groups. It is preferably a compound of formula: R 1 (Y), Si (X) 3, (I) in which the groups Y, identical or different, are monovalent organic groups bonded to silicon by a carbon atom, the groups X, which are identical or different, are hydrolyzable groups or hydroxyl groups, R 1 is a group comprising a polyoxyalkylene function, m is an integer equal to 0, 1 or 2. Preferably m = 0.
    [0017] The X groups are preferably chosen from alkoxy groups -O-R 3, where R 3 is an alkyl radical, linear or preferably branched C 1 -C 4, better C1, acyloxy -OC (O) R 4 where R 4 is a linear alkyl radical or branched, preferably C1-C6, preferably methyl or ethyl, halogens such as Cl and Br or trimethylsiloxy (CH3) 3SiO-, -NH2, -NHSiMe3, -NH-alkyl or dialkylamino groups in which the linear or branched alkyl groups are preferentially C 1 -C 6 (for example the groups -N (CH 3) 2 and -N (C 2 H 5) 2), and the combinations of these groups. Preferably, the groups X are alkoxy groups, and in particular methoxy or ethoxy, and better ethoxy.
    [0018] The group Y, present when m is not zero, is preferably a hydrocarbon group, saturated or unsaturated, linear or branched, preferably C 1 -C 10 and better still C 1 -C 4, for example an alkyl group, such as methyl or ethyl, a vinyl group, an aryl group, for example aromatic monocyclic or bicyclic, for example phenyl, optionally substituted, in particular with one or more C 1 -C 4 alkyl groups. Preferably Y represents the methyl group. 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 (R 1 group) preferably comprises less than 80 carbon atoms, preferably less than 60 carbon atoms, and more preferably less than 50 carbon atoms. The group R1 preferably satisfies these same conditions. The group R1 generally has the formula -L-R2, where L is a divalent group bonded 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 bonded to the group L through an oxygen atom, this oxygen atom being included in the group R2. Nonlimiting examples of L groups are linear or branched alkylene groups, preferably from C2 to C15, and better still from C2 to C15, and more preferably from C2 to 010, optionally substituted, a monocyclic or bicyclic C3-C10 group, cycloalkylene, preferably C3-C10 monocyclic or bicyclic arylene, carbonyl, amido, or combinations of these groups such as cycloalkylenealkylene, biscycloalkylene, biscycloalkylenealkylene, arylenealkylene, bisphenylene, bisphenylenealkylene, amido alkylene, an example of which is the group CONH (CH2) 3, or the groups -OCH 2 CH (OH) CH 2 - and -NHC (O) -. Preferred L groups are alkylene groups, preferably linear, preferably having 10 carbon atoms or less, more preferably 5 carbon atoms or less, for example ethylene and propylene.
    [0019] Preferred R2 groups include a polyoxyethylene - (CH2CH2O) n-, polyoxypropylene group, or combinations thereof. Preferred organosilanes of formula (I) are compounds of the following formula (II): Ym (X) 3, Si (CH 2) n - (L ') - (OR), - O- (L "), Where R 'is a hydrogen atom, an acyl group or an alkyl group, linear or branched, preferably C 1 -C 10 and better still C 1 to C 5 optionally substituted by one or more functional groups, and further comprising one or more double bonds, R is a linear or branched alkylene group, preferably linear, preferably comprising from 2 to 3 C, for example an ethylene or propylene group, L 'and L ", which are identical or different, are divalent groups , X, Y and m are as defined above, n 'is an integer ranging from 1 to 10, preferably from 1 to 5, n is an integer ranging from 3 to 50, preferably from 4 to 50, better from 4 to 30, more preferably from 5 to 25, m 'is 0 or 1, preferably 0, m "is 0 or 1, preferably 0. Groups L' and L", when present , can be cho isis among the divalent groups L previously described and preferably represent the group -OCH 2 CH (OH) CH 2 - or the group -NHC (O) -. In this case, the groups -OCH2CH (OH) CH2- or -NHC (O) - are connected to the adjacent groups (CH2) ,, (in the case of a group L ') and R' (in the case of a group L ") through their oxygen atom (for the group -OCH2CH (OH) CH2-) or through their nitrogen atom (for the group -NHC (0) -).
    [0020] The group -O- (L ")," - R 'is preferably an alkoxy group (m "= O, R' = alkyl), preferably a methoxy group, Preferably the compounds of formula (I) or (II) ) comprise a single silicon atom carrying at least one hydrolyzable group According to one embodiment, m = 0 and the hydrolysable groups X denote methoxy or ethoxy groups, n 'is preferably equal to 3. R 'denotes an alkyl group having less than 5 carbon atoms, preferably a methyl group, R' may also denote an aliphatic or aromatic acyl group, especially the acetyl group, and R 'may designate a trialkoxysilylalkylene group or trihalogénosilylalkylène such as the group - (CH2), "Si (R5) 3 the groups R5 being identical or different R5 is a hydrolyzable group such as groups X defined above and n" is an integer such as the group n 'defined above. An example of such a group R 'is the group - (CH 2) 3Si (OC2H5) 3 In this embodiment, the organosilane compound comprises two silicon atoms carrying at least one hydrolyzable group.
    [0021] According to preferred embodiments, n is 3, or varies from 6 to 9, from 9 to 12, from 21 to 24, or from 25 to 50, preferably from 6 to 9. Examples of compounds of formula ( II), mention may be made of 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane of the formulas CH 3 O- (CH 2 CH 2 O) 6 -9- (CH 2) 3 Si (OCH 3) 3 (III) and CH 3 O- (CH 2 CH 2 O) - (CH 2) 3 Si ( OCH 3) 3 (IV), sold by Gelest, Inc. or ABCR, the compound of formula CH 3 O (CH 2 CH 2 O) 3 (CH 2) 3 Si (OCH 3) 3 (Vila), more generally the compounds of formula CH 3 O (CH 2 CH 2 O) - (CH2) 3Si (OCH3) 3 where n varies from 4 to 45 (in particular n = 21, 22, 23 or 24), 2- [methoxy (polyethyleneoxy) propyl] trichlorosilanes, 21 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 the formula HO- (CH 2 CH 2 O) 6 -9- (CH 2) 3 Si (OC 2 H 5) 3, the compounds of the formulas HO- (CH 2 CH 2 O) 8 -12- (CH 2) 3 Si (OCH 3) 3 and HO- (CH 2 CH 2 O 8-12- (CH2) 3Si (OC2H5) 3, polypropylene-bis [(3-methyldimethoxysilyeropyl) oxide, and the two-headed siloxane compounds such as polyethylene-bis [(3-triethoxysilylpropoxy) -2-oxide) -hydroxypropoxy] 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): ## STR2 ## wherein CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 (CH 2) 3 Si (OC 2 H 5) 3 (V) 3Si (OC2H5) 3 (VI) (VII) (VIIa) CAS: 65994-07-2 Preferred families of compounds of formula (II) are those of [alkoxy (polyalkylenoxy) alkyl] trialkoxysilanes or their trihalogenated analogs (m = m m = 0, R '= alkoxy), the preferred compound being that of formula (III). Preferably, the compound A according to the invention does not have a fluorine atom. Preferably, the molar mass of the 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 still more preferably from 400 to 1000 g. / mol. The hydrophobic compound B bears at least one hydrophobic group. By "hydrophobic" groups is meant, in the context of the present invention, combinations of atoms that are not likely to associate with water molecules, especially by hydrogen bonding. These are generally nonpolar organic groups, free of charged atoms. Compound B preferably comprises at least one fluorinated group, preferably a perfluorinated group, typically a fluorocarbon group, preferably chosen from fluoroalkyl, fluoroalkenyl, perfluoroalkyl, perfluoroalkenyl, (poly) (fluoroalkyl ether), (poly) (perfluoroalkyl ether) groups. ), (poly) fluoroalkoxy [(poly) alkyleneoxy] alkyl, preferably fluoroalkyl. These linear, cyclic or branched groups may be directly connected to each other or via divalent groups, especially alkylene, alkenylene, oxygen atoms or nitrogen bridges (-NH-, -N = ). The fluorocarbon groups preferably comprise at least 50% of fluorine atoms to replace the hydrogen atoms of the hydrocarbon group from which they are derived, preferably at least 70% and (C2H50) 3Si (CH2) 30 (CH2CH2O) 25-30 (CH2) 3Si (0C2H5) 3 even better at least 90 `Vo. These groups may for example comprise units such as -CHF-, -CHF-CHF-, -CH2-C (CF3) 2-, -CF2-C (CF3) 2-, -CF2-, -CF2-CF2-, -CF2-CF2-CF2-, -CF2-C (CF3) 2-, - (CHF), -, - (CF2), -, n denoting an integer greater than or equal to 3. By poly (fluoroalkyl ether) group is meant a group resulting from the polymerization of fluoroalkoxy units or the copolymerization of these units with other units such as alkoxy units. Examples of such groups are - (CHF-CHF-0), -, - (CH2-CF2-O) n-, - (CF2-CF2-O) n-, - (CF2-CF2-CF2-O) n-, - (CF2-CH (CF3) -O) n-, - (CF2-CF (CF3) -O) n-, where n denotes an integer greater than or equal to 1. Such groups may also include units polyalkoxy such as - (CH2-CH2-O), -, - (CH2-CH2-CH2-O), - - (CH2-C (CH3) 2 -O), where m is an integer greater than or equal to 1 Compound B generally comprises at least one group capable of establishing a covalent bond with a functional group present on the external surface of the substrate or of the first coating on which it will be grafted, or present in compound A, said functional group being preferably a silanol group in the case where a first coating is present. This group, which is a reactive group, may be, without limitation, one of the following groups: an isocyanate group, acrylate, methacrylate, haloalkyl, carboxylic or sulfonic acid, acyl chloride, chlorosulfonyl, chloroformate, ester, an atom silicon bearing at least one hydrolyzable group (the hydroxyl group being considered here as a hydrolyzable group), or a group containing an epoxy function such as the glycidyl group, preferably a silicon atom bearing at least one hydrolyzable group, in particular a silanol group or a precursor thereof. Examples of hydrolyzable groups are X groups as defined above. Compound B is preferably an organosilane compound (this term especially including organosilazanes), better an organosilane compound having at least one (preferably one) silicon atom carrying at least one hydrolyzable group, more preferably an organosilane compound having at least one at least one hydrophobic group, especially fluoroalkyl, and at least one silicon atom bearing at least one hydrolyzable group, for example an organoalkoxysilane. According to one embodiment, the compound B comprises at least one -Si (R) 3 group, where R represents a hydrolysable group, in particular chosen from the groups -OCH3, -002H5, -OH and -NH2. Thus, compound B may for example be a silazane or include a trialkoxysilyl group. Preferably B has a trialkoxysilyl group. Preferably, its hydrophobic chain, for example fluoroalkyl, is functionalized at one end or at both ends, ideally at one end, by at least one, preferably one, group comprising at least one (preferably one) atom. silicon carrier of at least one hydrolyzable group. This organosilane compound preferably comprises a silicon atom bearing at least two hydrolyzable groups, preferably three hydrolyzable groups. Preferably, a single chain end of compound B comprises a silanol group or a silanol group precursor.
    [0022] Compound B can be chosen from silanes (or silazanes) of formulas (VIII) and (IX): ## STR2 ## (VIII) H (CH 2) g- (CF2) h- (CH2), - (CF2), - Si (R) 3 (IX) where each of c, d, e, f, g, h, i and j denotes an integer ranging from 0 to 10, at least one of c, d, e and f is other than 0, at least one of g, h, i and j is other than 0, and R is a hydrolyzable group as defined above. Preferably, c + d + e + f 15 and / or 5 g + h + i + j 15, and more preferably c + d + e + f 12 and / or 5 g + h + i + 12. A preferred component B is a silazane compound having a hydrolyzable Si-N bond, such as fluoroalkyl silazane of the formula CF 3 - (CF 2) 7 -CH 2 -CH 2 -Si (NH 2) 3 This compound is available under the name OF110TM from the company Optron Other B constituents that can be used are the fluorinated compound OF210TM from the same company and the compound marketed by Shin-Etsu Chemical under the name KP 911®. monolayer of 5 nm on a silica SiO 2 surface generally leads to a layer having a surface energy of less than or equal to 16 mJ / m 2, better still less than or equal to 15 mJ / m 2, and more preferably less than or equal to 14 mJ / m 2. Preferably, the molar mass of compound B according to the invention is less than or equal to 900 g / mol, more preferably less than or equal to 800 g / mol, better still less than or equal to 700 g / mol, and even better lower or equal to equal to 700 g / mol. It is preferably 300 to 800 g / mol, more preferably 300 to 700 g / mol, and still more preferably 400 to 600 g / mol. The precursor of the anti-fogging coating according to the invention, formed from at least one compound A preferably having a polyoxyalkylene group and at least one compound B preferably having a fluorocarbon group as defined above, also constitutes a anti-fouling coating. It generally makes it possible to lower the surface energy of the optical article to 25 mJ / m 2 or less. In the absence of hydrophilic compound A, the coating obtained does not have satisfactory anti-fogging properties, whereas in the absence of hydrophobic compound B, the coating obtained does not have satisfactory antifouling properties. According to one embodiment of the invention, the precursor of the anti-fog coating comprises more than 80% by weight of compound A and B according to the invention, relative to the total mass of the precursor of the anti-fog coating, preferably more than 90%. Vo. According to one embodiment, the anti-fogging coating precursor consists of a layer of said compounds A and B. Preferably, the anti-fogging 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 weight of the coating, better not understand. When the organosilane compound used for the formation of the anti-fogging coating is deposited under vacuum, preferably no metal oxide is co-evaporated with it, according to the technique of the co-evaporation of at least one organic compound and at least one an inorganic compound described in application EP 1324078. According to the invention, the deposition of compounds A and B forms a precursor coating of an anti-fog coating comprising an internal part in which said compounds A and / or B are grafted to the first coating ( when present), to the substrate, and / or to each other (at least in part) permanently (by means of a covalent bond and not by simple adsorption), and an external part removable by washing and / or wiping (mechanically and / or chemically). To achieve such a structure, it is possible to deposit an excess of compounds A and / or B on the surface of the first coating or of the substrate preferably comprising silanol groups, preferably an excess of compound A. The setting of the deposition parameters for to achieve such a configuration is within the reach of the skilled person. By excess, it is meant that a quantity of hydrophilic compound A, deposited after the compound B, and / or a part of the compound B, remained free, that is to say that it is not grafted by a covalent binding with either the first coating or the substrate, or with the compound A or B. The grafting of the compounds A and B on the surface of the substrate or the first coating includes the case where each of these two compounds is grafted covalently , directly, or only one of them, preferably compound B. According to one embodiment, when the compounds A and / or B are silanes whose silicon atom has at least one hydrolysable R group at least one of the Si-R groups of the compound A and / or the compound B is covalently bound to a hydroxyl group of the substrate or the first coating. The precursor coating of the anti-fog coating is a coating preferably having a thickness (before wiping) greater than or equal to 3 nm, more preferably 5 nm, more preferably 8 nm, and most preferably 10 nm. Its thickness is preferably less than 100 nm, better 50 nm and even better 20 nm. It is typically from 3 to 100 nm, preferably from 5 to 50 nm. The deposition of the compounds A and B on the surface of the first coating or of the substrate according to the invention can be carried out according to usual techniques, preferably by deposition in the gas phase or in the liquid phase, better in the gaseous phase, generally in a reaction chamber. Empty. The vapor phase deposition can consist of a physical vapor deposition (PVD) or a chemical vapor deposition (CVD), such as, without limitation, evaporation, possibly assisted by ion beam, sputtering, deposition plasma enhanced chemical vapor phase. The preferred method is physical vapor deposition, especially vacuum evaporation, generally combined with heating of the compounds to be evaporated. It can be put into play by using evaporation systems as diverse as a Joule effect heat source (the Joule effect is the thermal manifestation of the electrical resistance) or an electron gun, any other device known to the a person skilled in the art who can also be used. Compounds A and B can be dissolved beforehand in a solvent before being evaporated to better control the rate of evaporation and deposition.
    [0023] The hydrophilic compound A is preferably deposited by vacuum evaporation using a Joule effect heat source. The hydrophobic compound B is preferably deposited by evaporation under vacuum using an electron gun to cause its vaporization. The compounds A and B may be deposited successively, that is to say without overlapping the deposition steps of the one or the other compound or concomitantly (for example by coevaporation) or partially concomitant. These compounds are preferably deposited successively. The step of depositing the hydrophobic compound B is preferably begun before the step of depositing the hydrophilic compound A. According to the optimal embodiment, the formation of the precursor of the anti-fogging coating according to the invention by evaporation under vacuum is preferably carried out by successive deposition of a hydrophobic compound B and then a hydrophilic compound A. The duration of the deposition process and especially the evaporation is adjusted to obtain the desired coating thickness. The deposition conditions are chosen so that, after the deposition of the compounds A and B, a coating having a static contact angle with the water greater than 90 ° and a polar component of the energy of surface greater than 1.5 mJ / m2. The nature of the compounds employed, their respective amounts (which can be modulated by adjusting the evaporated flow rates), the order in which they are deposited and the duration of the deposition are examples of parameters that the person skilled in the art will be able to vary to achieve to the coating having the desired properties. Compounds A and B are preferably used during deposition in such quantities and conditions that, if deposited on separate supports, layers of compounds A and B would be formed in a ratio [hysical thickness of layer compound A] / [hysical layer thickness of compound B] less than 3, and preferably greater than 0.8. Compound A must be used in sufficient quantity so that the surface of the precursor coating of the anti-fog coating has a polar surface energy component of greater than 1.5 mJ / m 2. According to one embodiment of the invention, the deposition conditions are chosen so that the ranges of real physical thicknesses measured for each of its layers, measured in monolayer, are from 1 to 15 nm for the layer obtained from the hydrophobic compound B; 4-50 nm, preferentially 4 to 25 nm, for the layer obtained from the hydrophilic compound A. The measurements can be made by multi-wavelength ellipsometry.
    [0024] The precursor coating of the anti-fog coating can be obtained by directly depositing the appropriate amount of compounds A and B. However, the inventors have found that it is preferable to form the precursor coating of the anti-fog coating by depositing an excess of compounds A and B and predominantly an excess of hydrophilic compound A on the surface of the optical article, and removing the excess of these deposited but ungrafted compounds, so as to achieve the same desired final thickness. This procedure guarantees the anti-fog performance of treated lenses. The inventors have indeed found that when a layer of precursor coating is deposited directly without excess thickness, it is possible in certain cases to obtain an irregular deposit and an anti-fog coating precursor coating whose surface does not have sufficient affinity to to a liquid solution of surfactant, which leads to a coating that does not have the desired anti-fogging properties. After the deposition of compounds A and B according to the invention, the outer portion of the wipe-removable coating can be removed by washing and / or wiping or can undergo the removal technique described in WO 2012/153072. which involves the use of a temporary layer, in the case where such a temporary layer has been deposited. The outer portion of the precursor coating of the anti-fog coating is removable by washing and / or wiping, which means that it can be removed by, in particular, subjecting it to washing with soapy water (containing a surfactant) by means of a sponge then with deionized water, and / or wiping for typically 20 seconds or less, using a fabric CEMOITM, WypallTM or SelvithTM dry or optionally impregnated with alcohol, typically isopropyl alcohol. This wiping may possibly be followed by a new rinse with deionized water and final wiping with a cloth. After the removal of the surplus of compounds A and possibly deposited compounds B, that is to say of the outer part of the precursor coating of the wipe-removable anti-fog coating, it does not remain on the surface of the first coating according to the invention or the substrate that the inner portion of the precursor coating of the anti-fog coating containing the compounds A and B actually grafted. The ungrafted molecules are thus removed. The inner part of the precursor coating is not removable by means of a mild treatment such as dry wiping with a cloth or similar treatment, or wiping with a cloth impregnated with water, soapy water or an alcohol such as isopropyl alcohol. The invention also relates to a method for preparing an optical article as defined above, preferably an ophthalmic lens, comprising: a) providing a substrate having at least one main surface, b) depositing preferably by evaporation under vacuum on said main surface of the substrate or on a first coating, when said main surface of the substrate is coated with a first coating, at least one hydrophilic compound A and at least one hydrophobic compound B, so as to obtain a precursor coating of an anti-fog coating comprising an inner portion wherein said compounds A and B are grafted to the substrate or when present at the first coating, and an outer portion removable by washing and / or wiping. As explained above, the method of the invention comprises steps of exposing the main surface of the substrate or the first coating to compound A and / or compound B, generally in a vacuum chamber, causing the deposition of this or these compounds. The method of the invention may also comprise an additional step of deposition of at least one surfactant on the surface of the precursor coating of the anti-fogging coating obtained after removal of the outer portion of the precursor coating from the wipe-removable anti-fog coating, thereby providing access to a temporary anti-fog coating. This surfactant film provides the lenses with temporary protection against fogging by creating a uniform layer on their surface that helps disperse the water droplets on the glass surface so that they do not form visible fogging.
    [0025] According to one embodiment, the surfactant is deposited by applying a film of a liquid solution containing at least one surfactant. The application of the surfactant solution may be carried out by any known technique, in particular by soaking, centrifugation or spraying. The surfactant solution is preferably applied by depositing a drop of this solution on the surface of the precursor of the anti-fog coating and then spreading it so as to cover preferably all of said precursor coating. 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 surfactants. A commercially available surfactant solution to confer anti-fogging properties is Essilor's Optifog TM Activator solution.
    [0026] According to another embodiment, which is preferred, the surfactant is applied to the precursor coating by means of a fabric impregnated with said surfactant, for example a dry or wet wipe, preferably reusable. It is ideally a dry wipe, that is to say having a dry appearance to the touch. These impregnated fabrics are capable of effectively dispensing the surfactant on the surface of a substrate, by simply wiping the surface to be treated (reciprocating movements in translation and / or rotation). The fabric impregnated with surfactant according to the invention is preferably a microfiber fabric, more preferably woven or knitted, better knitted. The fabric used in the invention preferably comprises at least 80% by weight of microfibers, better still at least 90% by weight of microfibres, preferably at least 95% by weight, better 100% by weight of microfibers. By microfibers is meant textile fibers whose linear density is less than 1.3 decitex (1.3 g / 10 km). The microfiber fabric preferably comprises hydrophilic polymer microfibers and lipophilic polymer microfibers, especially polyamide microfibers and polyester microfibers, more preferably 60 to 85% by weight polyester microfibers and 15 to 40% by weight. of polyamide microfibres. An example of such a fabric is Cemol ™ fabric, consisting of 69.5% by weight of polyester microfibers and 30.5% by weight of polyamide microfibres.
    [0027] The wipe according to the invention comprises a fabric preferably impregnated with 5 to 40% by weight of surfactants relative to the mass of the non-impregnated fabric, preferably from 10 to 40% by weight, better still from 15% to 35% by weight. and optimally from 20 to 30% by weight. The impregnated fabrics and wipes that can be used to impart anti-fogging properties to a substrate, as well as their method of preparation, are described in more detail in the application filed under No. FR 2013-50459. The surfactant employed must be able to confer on the optical article anti-fogging properties after application to its surface, which can be verified by carrying out the hot vapor test described in the experimental part. A wide variety of surfactants can be used for direct application by means of a solution or via a wipe. These can be ionic (cationic, anionic or amphoteric) or nonionic, preferably nonionic or anionic. However, a mixture of surfactants belonging to these different categories is possible. Examples of surfactants which can be used are those disclosed in applications WO 2013/013929 and FR 2013-50459. Mention may be made of alkyl monoethers of polyethylene glycols, surfactants having a sorbitan ring and in particular polyoxyalkylene sorbitan fatty acid esters, triblock copolymers comprising two ethylene oxide blocks and a central oxide block. propylene, the compounds of fluoroalkyl polyethoxylated nature. Preferably, a surfactant comprising a poly (oxyalkylene) group, more preferably a polyoxyalkylene group having more than 6 oxyalkylene units, and more preferably a polyoxyethylene group having more than 6 oxyethylene units, is used. The surfactant used preferably has a hydrophilic / lipophilic balance (HLB) k 5, which is preferably less than or equal to 18, better still less than or equal to 16 and even more preferably less than or equal to 15, so as to benefit from optimum anti-fogging properties. . The term hydrophilic / lipophilic balance (in English HLB, for "Hydrophilic Lipophilic Balance") is well known to those skilled in the art and represents a characteristic quantity of a surfactant, which is even greater than the solubility in the surfactant water is high. In the present application, the theoretical (calculated) value of the hydrophilic / lipophilic balance will be taken into account. The calculation methods to be employed, according to the category of surfactant, are indicated in the application FR 2013-50459.
    [0028] The anti-fog coating of the invention obtained after the application of the surfactant to the surface of the substrate preferably has a static contact angle with the water of less than or equal to 10 °, more preferably less than or equal to 5 °. It usually constitutes the outer coating of the optical article.
    [0029] The invention also relates to an assembly comprising an optical article having a substrate coated with a precursor coating of an anti-fog coating whose surface has a static contact angle with water greater than 90 ° and a polar component of surface energy greater than 1.5 mJ / m 2, and a surfactant preferably having a hydrophilic / lipophilic balance (HLB) k 5, the assembly preferably comprising a fabric impregnated with said surfactant, better a dry wipe comprising a microfiber cloth impregnated with said surfactant. The following examples illustrate the invention in a more detailed but nonlimiting manner. Unless otherwise indicated, all thicknesses in the present application are physical thicknesses, measured by multi-wavelength ellipsometry, after deposition. EXAMPLES 1. Materials and optical articles used Hydrophilic organosilane compounds A used in the examples to form the precursor of the anti-fog coating are 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane having 6 to 9 ethylene oxide units of formula (III) and 450-600 g / mol molar mass (CAS No. 65994-07 -2, Ref: SIM6492.7, supplied by Gelest, Inc.), the compound of formula CH3O (CH2CH2O) 9-12- (CH2) 3Si (OCH3) 3 (IV), supplied by Gelest, Inc. and the compound of the formula CH3O (CH2CH2O) 21-24- '- (CH3Si (OCH3) 3 (IVa), supplied by Gelest (Reference: SIM6492.73) The hydrophobic organosilane compound B used in the examples for form the precursor of the anti-fog coating is the fluorinated compound OF210TM provided by the Other hydrophobic compounds used in the comparative examples are Optool DSXTM (Daikin Industries), and KY-130TM (Shin-Etsu Chemical). The vacuum evaporation device for depositing the different layers (antireflection, precursor coating of the anti-fog coating) is a Syrus III machine with two material evaporation systems, an electron gun evaporation system and a system of evaporation. Joule effect evaporation.
    [0030] The glasses used in the examples according to the invention comprise a polycarbonate lens substrate of bisphenol A (correction -8.00 dioptres, +2.00 cylinder), comprising on each of its faces a shockproof polyurethane primer of a thickness of the order of 1 micron, itself coated with an anti-abrasion coating with a thickness of about 3 microns and a five-layer anti-reflective coating ZrO 2 / SiO 2 / ZrO 2 / ITO / SiO 2. other deposition conditions and the treatments they have undergone are described in more detail in the experimental part of the application WO 2012/153072.
    [0031] The same ophthalmic lens glasses are also reproduced, but without power (two same diopters on the front face (Convex) and rear (concave) for haze measurement) 2. Deposition of the precursor of the anti-vapor vapor coating The different chemical compounds used to Anti-fog coating precursors are initially packaged in copper capsules equipped with iron straw to limit the product projections during Joule evaporation or via an electron gun Each capsule, containing 100 to 300 1..11 of compound, according to the desired thickness, is preheated on a heating plate at 70 ° C. for 2 minutes before the evaporation step, this makes it possible to evaporate the possible solvents and to degas the product. OF210TM, used pre-conditioned in copper capsule with iron straw, does not require a preheating step Capsules containing hydrophobic compounds, comp arative or according to the invention, are further covered with a perforated Tantalum lid holes obtained from the company Satis to avoid a direct impact of the electron gun on these compounds during their evaporation. The lid is heated by the flow of electrons which itself heats the copper capsule by thermal conduction. The temperature increases in the "oven" thus created, until the evaporation of the compound.
    [0032] The deposition of the precursor of the anti-fog coating according to the invention on the antireflective coating of the glasses is carried out in two stages. In a first step, the hydrophobic compound B (OF210TM) is deposited by evaporation under vacuum using an electron gun evaporation system in which the copper capsules containing the compounds to be evaporated (speed: varying by more than 0) are placed. nm / s at 0.5 nm / s, usually 0.25 nm / s, emission current varying from 1 to 4 mA, circular and wide electron scanning pattern, mean residual pressure: 7.9.10-4 Pa), then the hydrophilic compound A (compound of formula III) is deposited by vacuum evaporation using a Joule effect heat source, namely a metal nacelle traversed by an electric current in which the copper capsules containing the compounds are deposited. to be evaporated (speed: varying from more than 0 nm / s to 0.5 nm / s, generally 0.25 nm / s, heating current ranging from 2 to 5.5 A, average residual pressure: 5.7 × 10- 4 Pa). In the examples, different amounts of compounds A and B were evaporated. The thickness ratio indicated in Table 1 below was calculated by dividing theoretical physical thicknesses, corresponding to the thicknesses of coatings that would have been obtained if the various compounds involved had been deposited on separate supports. Indeed, the two compounds evaporated successively are likely to react with each other and lead to a final coating of real thickness different from the sum of the theoretical thicknesses of the two deposited layers.
    [0033] An anti-fog coating precursor coating having a thickness of the order of 10 to 17 nm (thicknesses measured with a multi-wavelength ellipsometer, including the excess of siloxane compound) is obtained. In the comparative examples, two compounds are successively evaporated (with the exception of Comparative Examples 1 and 8 where only one compound is evaporated), to form coatings with a thickness comparable to that of Example 1. Hydrophobic compounds (OF210TM , Optool DSXTM, KY-130TM) were evaporated by means of the electron gun, while the hydrophilic compound (III) was evaporated by the Joule effect, except for Comparative Example 5 where the two compounds (hydrophobic and hydrophilic) were have been evaporated by Joule effect.
    [0034] At the end of the evaporation, the surface of each glass is rinsed with soapy water, tap water, isopropyl alcohol, tap water, then deionized water and wiped with a dry CemiTM fabric so that the surplus of deposited siloxane compounds is removed. The CémoiTM fabric designates a fabric supplied by the supplier Facol under the reference Microfibre M8405 30x40.
    [0035] The measurements of surface properties of the glasses (contact angle, surface energy) giving the results indicated in Table 1 are made at this stage, on the lenses thus washed and wiped. The surface energy characteristics were determined using a Owens-Wendt DIGIDROP GBX apparatus described in the reference: "Estimation of the surface force energy of polymers" Owens DK, Wendt RG (1969), J. Appl. Polym. Sci., 13, 1741-1747 using two reference liquids (water and diiodomethane, needle of internal diameter 0.15 mm). This device also allows the determination of static contact angles from a photograph taken at a given moment (3000 ms) after the deposition of a drop of liquid (here, water). 3. Formation of the temporary anti-fog coating and evaluation of its performance The two sides of the glasses are wiped with a cloth of CémoiTM fabric impregnated with surfactant (Capstone® FS 3100, 30% by mass) by making a spiral movement from the center to the edge with the wipe, so as to "charge" them in surfactant. This corresponds to an application. Different levels of application can be achieved, for example 5, 10 or 20 applications. The glasses are then placed for 24 hours in a temperature controlled environment (20-25 ° C) and at a humidity of 50%, then placed 15 seconds above a heated container containing water at 55 ° C (test hot steam). Immediately afterwards, a visual acuity scale at 5 m is observed through the tested glass. The test is considered successful if an observer with a vision of 10/10 and having the glass placed in front of his eye obtains a visual acuity of 10 / 10th (in transmission, table Optotype of Snellen placed at 5 meters, Armaignac Tridents scale, ref T6 available from FAX INTERNATIONAL), and observes neither fogging nor visual distortion. This test simulates the living conditions where a wearer places his face over a cup of tea, coffee or a pot of boiling water. The results obtained are shown in Table 1. In Examples 1 to 5, the anti-fogging properties were obtained for a surfactant application level ranging from 5 to 15, whereas the glass of Example 6 required about 20 applications. The glasses of Comparative Examples 1 to 5 did not exhibit any anti-fogging properties even after 20 surfactant applications. Comparative Example 1 shows that if no hydrophilic compound A is used to form the outer coating, this glass has anti-fouling properties but no anti-fogging properties, and that the hydrophobic compound B is deposited by Joule effect or under the action an electron gun. Only the glasses of Examples 1 to 5 according to the invention have both anti-fogging and anti-fouling properties. Table 1 Example First Second Ratio 2nc Compound EP AND Perf. Perf. evaporated / 1st compound (rnJ / rn2) ED (mJ / m2) contact evaporated anti-fogging compound (mJ / m2) with water (-) (*) (°) 1 OF210TM Co mpo se (III) 2,66 3 , 3 20.7 24 93 +++ Yes 2 OF210TM Co mpo se (III) 2.15 2.7 19.2 21.9 97 +++ Yes 3 OF210TM Compound (III) 1.35 2.1 19, 4 21.5 99 +++ Yes 4 OF210TM Compound (IV) 2.30 3.2 20.2 23.4 94 +++ Yes 5 OF210TM C omposed (IVa) 1.93 2.4 19 21.4 98 +++ Yes 6 OF210TM Compound 0.90 1,8 19,1 20,9 100 +++ Yes 7 OF210TM Co mpo se (III) 1 2,3 17,6 19,9 100 +++ Yes Comp. 1 OF210TM (2 nm - 0.9 16.4 17.3 107 +++ No thick) Comp. 2 Optool Compound (III) 4 0.6 14.3 14.9 110 +++ No DSXTM Comp. 3 KY- Compound (III)> 1 <1.5 111 +++ No 130TM Comp.4 OF210TM Co mpo se (III) 0.73 1.3 15.3 16.6 105 +++ No Comp.5 OF210TM Compound 1 , 9 0.9 19.6 20.5 104 +++ No III Comp. 6 Compound (III) OF210TM na na na na 42-70 + Yes Comp. 7 Compound (III) Optool na na na na 35-50 + Yes DSXTM Comp. 8 1 nm - 23.2 29.3 52.5 42.5 + Yes Compound III) ((-2) epsseur) Ep and E: Polar and dispersive components of the surface energy of the anti-fog coating precursor, AND designating the total energy. (*) Physical thickness ratio. (**) After application of a surfactant solution. (***) Thickness including excess siloxane compound. na: not measured.
    [0036] The anti-fouling behavior of an ophthalmic lens according to the invention Example 7 with regard to soiling is detailed below, in comparison with ophthalmic lenses of the prior art (lenses of comparative examples Comp. Comp 8). + indicates that the antifouling properties of the lens are of the same order as the lens of Comparative Example 8 taken as a reference. +++ indicates that the lens has antifouling properties superior to that of the lens of Comparative Example 8 taken as a reference (Haze Level lower than 3.9%) after two rotations (according to the cleanability protocol described below) according to test No. 1 (CEMOI fabric) Method Procedure / Cleanability The test is carried out in a temperature-controlled room at 22 ° C. ± 1-3 ° C. and at an ambient humidity of 50% + 1-10% A stain is obtained by applying to the center of the glass a fingerprint previously impregnated with artificial sebum (consisting mainly of oleic acid) .The stain obtained (artificial sebum) is in the form of a stain. The glasses are then automatically wiped with microfiber cloth, impregnated or not, fixed to a mechanical robot, under a load of 750 g (movement of back and forth perfectly reproducible) A request Wiping is a one-way or a return of the fabric. The total movement during the movement of the fabric on the lens is 40 mm, or 20 mm on either side of a point centered on the dirt. The textile is always applied in the same direction against the glass. The movement starting from the center during the first movement and the value of 2 which is mentioned during the very first displacement is actually 1.5. The value of the diffusion rate in transmission (Haze, noted H) through the lens is measured with a Hazeguard XL 211 Plus device, the first measurement carried out in the center of the glass on an area covered by the sebum, then after a number of requests. wiping ratio of 2, 5, 10, 20 or 30 (the values mentioned are cumulative values since the beginning of wiping). The diffusion rate H is obtained according to ASTM standard D1003 "Standard test method for haze and luminous transmittance of transparent plastics", simultaneously measuring the total amount of light transmitted by the glass (total I) and the amount of diffuse light. , in transmission (diffuse I: amount of light transmitted and deviated by an angle greater than 2.5 ° from the normal direction): H (%) = / diffuse x100 total I The faster the haze is, the faster the cleaning and high cleanability. Test No. 1: The cleaning efficiency of the ophthalmic lens of Example 7 according to the invention was tested according to the preceding protocol with a CEMOITM tissue. FIG. 1 shows that: the ophthalmic lens according to the invention is much less the surface of the lens of Comparative Example 8 which is a lens whose surface comprises a state of the art anti-fogging precursor. Indeed, a fingerprint generates much more Haze in the case of Comparative Example 8 than in the case of Example 7 according to the invention. the ophthalmic lens according to the invention is cleaned much faster than a lens according to Comparative Example 8 and cleans as well as the ophthalmic lens of Comparative Example 1 only coated with the anti-fouling coating of OF210TM. The Haze is reduced by a factor of 8 from the first cleaning cycle (2 rotations) Test # 2: Test # 1 is repeated, except that a CEMOITM dry touch cloth impregnated with 30% by weight of CapstoneTM FS 3100 is used.
    [0037] FIG. 2 shows that the ophthalmic lens according to the invention is better cleaned than a lens according to the two comparative examples, in particular with respect to the lens of Comparative Example 8, the invention is superior. Test No. 3: Test No. 2 is reproduced except that, after applying the fingerprint, surface treatment of the ophthalmic lenses is performed with a dry touch CEMOITM fabric comprising 30% by weight of CapstoneTM FS. 3100 (5 rotations). Thus, anti-fogging ophthalmic lenses are tested with a very thin layer of Capstone ™ FS 3100 on their surface. FIG. 3 shows that the ophthalmic lens according to the invention has cleaner properties than those of a lens according to the invention. comparative example 8.
    权利要求:
    Claims (17)
    [0001]
    REVENDICATIONS1. An optical article having a substrate coated with a precursor coating of an anti-fog coating, characterized in that its surface has a static contact angle with the water greater than 90 ° and a polar component of the upper surface energy at 1.5 mJ / m2.
    [0002]
    Optical article according to claim 1, characterized in that the polar component of the surface energy is greater than or equal to 1.7 mJ / m 2, more preferably greater than or equal to 2 mJ / m 2.
    [0003]
    3. Optical article according to any one of the preceding claims, characterized in that the precursor coating of the anti-fog coating has a static contact angle with the water greater than or equal to 95 °, preferably greater than or equal to 100 ° .
    [0004]
    4. An optical article according to any one of the preceding claims, characterized in that the precursor coating of the anti-fog coating is formed of a material containing fluorocarbon groups and polyoxyalkylene groups.
    [0005]
    5. An optical article according to any one of the preceding claims, characterized in that the precursor coating of the anti-fog coating is formed by deposition of at least one hydrophilic compound A and at least one hydrophobic compound B.
    [0006]
    6. An optical article according to claim 5, characterized in that the compound A is an organosilane comprising at least one polyoxyalkylene group and having at least one silicon atom bearing at least one hydrolyzable group.
    [0007]
    7. An optical article according to any one of claims 5 or 6, characterized in that the compound B is an organosilane comprising at least one fluorocarbon group and having at least one silicon atom carrying at least one hydrolyzable group.
    [0008]
    8. An optical article according to any one of the preceding claims, characterized in that the precursor coating of the anti-fog coating is coated with a film of surfactant.
    [0009]
    9. An optical article according to any one of the preceding claims, characterized in that the precursor coating of the anti-fog coating has a surface energy of less than or equal to 25 mJ / m2.
    [0010]
    10. Optical article according to any one of the preceding claims, characterized in that it constitutes an ophthalmic lens.
    [0011]
    11. A method of preparing an optical article according to any one of the preceding claims, comprising: a) providing a substrate having at least one main surface, b) depositing on said main surface of the substrate at least one hydrophilic compound A and at least one hydrophobic compound B, so as to obtain a precursor coating of an anti-fog coating whose surface has a static contact angle with the water greater than 90 ° and a polar component of the surface energy greater than 1 5 mJ / m2.
    [0012]
    12. The method of claim 11, characterized in that the compounds A and B are deposited by evaporation under vacuum.
    [0013]
    13. The method of claim 12, characterized in that the compound A is deposited by vacuum evaporation using a Joule heat source and in that the compound B is deposited by evaporation in vacuo using an electron gun.
    [0014]
    14. Method according to any one of claims 11 to 13, characterized in that the precursor coating of the anti-fog coating is formed by successive deposition of compound B and compound A.
    [0015]
    An assembly comprising: - an optical article having a substrate coated with a precursor coating of an anti-fog coating, characterized in that its surface has a static contact angle with the water greater than 90 ° and a polar component surface energy greater than 1.5 mJ / m 2, and - a surfactant preferably having a hydrophilic / lipophilic balance (HLB) k 5.
    [0016]
    16. The assembly of claim 15, comprising said optical article and a fabric impregnated with said surfactant.
    [0017]
    An assembly according to any of claims 15 or 16, comprising said optical article and a dry wipe comprising a microfiber cloth impregnated with said surfactant.
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    同族专利:
    公开号 | 公开日
    JP2017510825A|2017-04-13|
    WO2015082521A1|2015-06-11|
    CA2932497A1|2015-06-11|
    CN105793762B|2020-06-02|
    KR102299913B1|2021-09-10|
    CN105793762A|2016-07-20|
    US10642072B2|2020-05-05|
    FR3014210B1|2016-01-01|
    EP3077857B1|2020-05-20|
    US20160306198A1|2016-10-20|
    KR20160093008A|2016-08-05|
    JP6825907B2|2021-02-03|
    EP3077857A1|2016-10-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2006049020A1|2004-11-01|2006-05-11|Daikin Industries, Ltd.|Composition for treating glass base|
    FR1350459A|1963-03-13|1964-01-24|Bright iris aperture graduation lens mount|
    US4467073A|1982-10-20|1984-08-21|Hydromer, Inc.|Transparent anti-fog coating compositions|
    US6183872B1|1995-08-11|2001-02-06|Daikin Industries, Ltd.|Silicon-containing organic fluoropolymers and use of the same|
    FR2824821B1|2001-05-17|2003-08-29|Essilor Int|PROCESS FOR THE PREPARATION OF A GLASS SUITABLE FOR OVERFLOWING, GLASS THUS OBTAINED AND METHOD FOR OVERFLOWING SUCH A GLASS|
    EP1324078A3|2001-12-28|2004-01-14|Hoya Corporation|Hybrid film, antireflection film comprising it, optical product, and method for restoring the defogging property of hybrid film|
    FR2834712B1|2002-01-14|2004-12-17|Essilor Int|PROCESS FOR TREATING OPHTHALMIC GLASS|
    US6849314B2|2002-04-18|2005-02-01|3M Innovative Properties Company|Fluoropolymer blends and multilayer articles|
    JP2004143443A|2002-09-30|2004-05-20|Toto Ltd|Hydrophilic coating composition, and dewing inhibitor and dewing inhibition method using it|
    JP4293593B2|2003-04-11|2009-07-08|東海光学株式会社|Antifogging optical body and method for forming antifogging layer on optical body|
    JP4581608B2|2003-12-02|2010-11-17|セイコーエプソン株式会社|Thin film manufacturing method, optical component manufacturing method, and film forming apparatus|
    JP4378565B2|2004-03-26|2009-12-09|株式会社ネオス|Alkoxysilane compounds|
    FR2901552B1|2006-05-26|2008-07-11|Essilor Int|OPTICAL ARTICLE COMPRISING AN EXTERNAL HYDROPHOBIC AND / OR OLEOPHOBIC COATING COATED WITH A TEMPORARY LAYER|
    FR2907915B1|2006-10-31|2009-01-23|Essilor Int|OPTICAL ARTICLE COMPRISING ANTI-SOIL COATING|
    JP2008152085A|2006-12-19|2008-07-03|Hoya Corp|Method for manufacturing spectacle lens, film deposition apparatus for spectacle lens, and spectacle lens|
    JP5085973B2|2007-04-26|2012-11-28|ゼネラル株式会社|Inkjet ink|
    FR2924233A1|2007-11-23|2009-05-29|Essilor Int|OPTICAL ARTICLE COMPRISING A TEMPORARY LAYER OF ALIPHATIC THERMOPLASTIC POLYURETHANE AND APPLICATION TO DEPOSITION|
    US8060969B2|2008-01-10|2011-11-22|Alpine Innovations, Llc|Cloth accessory with removable insert|
    JP2009175500A|2008-01-25|2009-08-06|Hoya Corp|Method for manufacturing optical member|
    JP2009226729A|2008-03-21|2009-10-08|Fujifilm Corp|Anti-fogging film|
    FR2943798B1|2009-03-27|2011-05-27|Essilor Int|OPTICAL ARTICLE COATED WITH AN ANTIREFLECTIVE OR REFLECTIVE COATING COMPRISING AN ELECTRICALLY CONDUCTIVE LAYER BASED ON TIN OXIDE AND METHOD OF MANUFACTURE|
    FR2954832A1|2009-12-31|2011-07-01|Essilor Int|OPTICAL ARTICLE COMPRISING A TEMPORARY ANTIBUID COATING WITH IMPROVED DURABILITY|
    WO2011095626A2|2010-02-08|2011-08-11|Essilor International |Optical article comprising an anti-reflecting coating having anti-fogging properties|
    JP6100242B2|2011-05-12|2017-03-22|エシロール アテルナジオナール カンパニー ジェネラーレ デ オプティックＥｓｓｉｌｏｒ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃｏｍｐａｇｎｉｅ Ｇｅｎｅｒａｌｅ Ｄ’ Ｏｐｔｉｑｕｅ|Optical article comprising a precursor coating of an antifogging coating and a temporary layer suitable for edging|
    KR101852652B1|2011-07-06|2018-04-26|도카이 옵티컬 컴퍼니 리미티드|Haze-proof optical article and method for producing same|
    WO2013013929A1|2011-07-22|2013-01-31|Essilor International |Optical article comprising a surfactant-based temporary antifog coating with an improved durability|
    WO2014102271A1|2012-12-28|2014-07-03|Essilor International |Method for the production of an optical article with improved anti-fouling properties|
    WO2014102298A1|2012-12-28|2014-07-03|Essilor International |Method for the production of an optical article with improved anti-fouling properties|
    FR3001117B1|2013-01-18|2015-03-06|Essilor Int|DRY WIPES WITH ANTIBUOUS AND / OR CLEANING ACTION|FR3042500B1|2015-10-14|2020-02-14|Essilor International|OPTICAL ARTICLE HAVING A PRECURSOR COATING OF AN ANTI-FOG COATING HAVING ANTI-FOULING PROPERTIES OBTAINED FROM AN AMPHIPHILIC COMPOUND|
    JP6085699B1|2016-03-15|2017-02-22|日本ペイント・インダストリアルコ−ティングス株式会社|Antifouling coating composition, method for forming antifouling coating layer, and method for producing ceramic building materials.|
    WO2018234841A1|2017-06-21|2018-12-27|Nikon Corporation|Nanostructured transparent article with both hydrophobic and antifog properties and methods for making it|
    WO2020016708A2|2018-07-18|2020-01-23|3M Innovative Properties Company|Vehicle sensors comprising repellent surface, protective films, repellent coating compositions, and methods|
    法律状态:
    2015-12-17| PLFP| Fee payment|Year of fee payment: 3 |
    2016-12-27| PLFP| Fee payment|Year of fee payment: 4 |
    2017-12-27| PLFP| Fee payment|Year of fee payment: 5 |
    2019-12-26| PLFP| Fee payment|Year of fee payment: 7 |
    2020-12-27| PLFP| Fee payment|Year of fee payment: 8 |
    2021-12-27| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362048A|FR3014210B1|2013-12-03|2013-12-03|OPTICAL ARTICLE COMPRISING A PRECURSOR COATING OF AN ANTI-BRATED COATING HAVING ANTI-GLASS PROPERTIES|FR1362048A| FR3014210B1|2013-12-03|2013-12-03|OPTICAL ARTICLE COMPRISING A PRECURSOR COATING OF AN ANTI-BRATED COATING HAVING ANTI-GLASS PROPERTIES|
    CA2932497A| CA2932497A1|2013-12-03|2014-12-03|Optical article comprising a coating that is a precursor of an antifog coating having antifouling properties|
    EP14809345.3A| EP3077857B1|2013-12-03|2014-12-03|Optical article having a precursor antifog coating having antifouling properties|
    KR1020167014537A| KR102299913B1|2013-12-03|2014-12-03|Optical article comprising a coating that is a precursor of an antifog coating having antifouling properties|
    JP2016536777A| JP6825907B2|2013-12-03|2014-12-03|An optical article containing a coating that is a precursor of an antifogging coating having antifouling properties.|
    US15/101,364| US10642072B2|2013-12-03|2014-12-03|Optical article comprising a coating that is a precursor of an antifog coating having antifouling properties|
    PCT/EP2014/076357| WO2015082521A1|2013-12-03|2014-12-03|Optical article comprising a coating that is a precursor of an antifog coating having antifouling properties|
    CN201480065706.4A| CN105793762B|2013-12-03|2014-12-03|Optical article comprising a coating having anti-soiling properties as precursor of an anti-fogging coating|
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