Optical lens with interference coating and multilayer system for improved wear resistance - Patents.com

Abstract

The present invention relates to an optical lens including a substrate having a front principal surface and a rear principal surface, at least one of which is successively coated with a multilayer interference coating including a first high refractive index sheet, a second low refractive index sheet, a third high refractive index sheet, a single sublayer having a thickness of 100 nm or more, and a stack of at least one high refractive index layer and at least one low refractive index layer, without including any Ta2O5 layer. UV weighted by the function W(λ) defined in the ISO 13666:1998 standard is lower than 10% at an incidence angle of 35°.

Description

[Technical field]

[0001] The present invention relates to optical articles, particularly ophthalmic lenses, comprising a substrate coated with a multilayer transparent interference coating, typically an anti-reflective coating, having improved abrasion resistance and good heat resistance, and to a method for producing such optical articles. [Background technology]

[0002] It is common practice in the art to coat at least one major surface of an optical substrate with multiple coatings to impart additional or improved optical or mechanical properties to the finished product. These coatings are commonly referred to as functional coatings.

[0003] Various coatings that may be used to impart multiple mechanical and / or optical properties may be impact resistant coating layers, abrasion and / or scratch resistant coating layers, anti-reflective and / or reflective coating layers, and / or anti-soiling and / or anti-fog layers.

[0004] Various methods can be found in the literature to improve the abrasion resistance of optical articles that are susceptible to environmental scratches.For example, it is proposed to use a relatively thick sublayer under the antireflective coating, or to increase the total thickness of the antireflective coating, as in JP2003-195003 and JP2003-294906, which describes a lens coated with a seven-layer antireflective coating, including a primer coating, a hard coat, and alternating layers of SiO2 and TiO2, the latter being deposited by ion-assisted deposition and known to be prone to photodecomposition.JP2003-294906 advises to control the thickness of the first three layers of the antireflective coating (counting from the substrate side) and to use a high ratio of (sum of physical thickness of SiO2 layers) / (sum of physical thickness of TiO2 layers) calculated for the first three layers.

[0005] US Pat. No. 8,982,466 relates to an optical lens having a hard coat and a multi-layer anti-reflection coating, together with a high refractive index layer made from TiO2, and having a thickness of less than 40 nm.

[0006] EP 2775341 discloses an ophthalmic lens having a hard coat layer, a 360-390 nm thick SiO2 sublayer, and a four-layer interference coating made of SiO2, ZrO2, and / or Ta2O5, which have a specific nanoindentation hardness and compressive stress, and which are typically deposited by ion-assisted deposition, a deposition technique that increases the compressive stress and can result in delamination.

[0007] JP 2002-122820 describes a hard-coated substrate coated with a SiO2 sublayer with a physical thickness of 89-178 nm (optical thickness: 0.25-0.5 λ at 520 nm) and a four-layer anti-reflection coating (ZrO2 / SiO2 / ZrO2 / SiO2). According to this document, a high critical temperature can be reached by balancing the thickness and stress of the coating between the layers of different materials. However, the only parameter investigated was the thickness of the sublayer. Its thickness should be such that the ratio (sum of physical thicknesses of SiO2 layers including sublayers) / (sum of physical thicknesses of ZrO2 layers) is in the range of 2-3. A high ratio is considered undesirable as it reduces the durability of the anti-reflection coating.

[0008] U.S. Pat. No. 7,692,855 discloses an optical article having antireflective properties and high heat resistance, comprising a substrate having at least one major surface coated with a multilayer antireflective coating in which the ratio of physical thickness of the low refractive index layer / high refractive index layer is typically greater than 2.1.

[0009] US 2008 / 206470 A1 relates to a method for producing an optical article having anti-reflective or reflective properties, including a sub-layer, a sub-layer, and a multi-layer stack. To increase the abrasion resistance of the optical article, the sub-layer must be deposited in a vacuum chamber with additional gas supplied during the deposition process, and an ion bombardment treatment must be performed on the exposed surface of the sub-layer before depositing the multi-layer stack.

[0010] In WO 2018 / 192998, it is proposed to control the thickness of the layers in the interference coating, i.e. to use a ratio of physical thickness of the outer low refractive index layer / outer high refractive index layer of 2 or more, in order to increase the wear resistance of the optical article. Furthermore, the optical article may comprise an impedance coating to limit interference fringes. Typically, in this case, the impedance coating comprises a SiO2 layer of 4 to 50 nm thickness and a ZrO2 or Ta2O5 layer of 4 to 15 nm thickness in contact with a sublayer, deposited in this order on the substrate, which is optionally coated. Summary of the Invention [Problem to be solved by the invention]

[0011] The object of the present invention is to provide a transparent optical article comprising an organic or inorganic glass substrate with an interference coating, preferably a lens, more preferably an ophthalmic lens for spectacles, with improved abrasion resistance, good adhesion to the substrate, and good resistance to heat and temperature changes (i.e. high critical temperature), which would be an alternative to optical articles with already known reflective or anti-reflective coatings. These properties must be obtained without compromising the optical and other mechanical performances of said article, such as the anti-reflective or reflective performance.

[0012] Another object of the present invention is to provide a method for manufacturing the above defined article, which can be easily integrated into a conventional manufacturing chain and which will avoid heating of the substrate. [Means for solving the problem]

[0013] The inventors have found that these objectives can be achieved by using a particular combination of layers deposited under a thick sublayer of an interference coating, which makes it possible in particular to increase the wear resistance of the optical article without compromising the adhesion properties of the interference coating.

[0014] Compared to conventional interference coatings, the interference coatings of the present invention have higher abrasion resistance, better adhesion, and similar or improved critical temperatures.

[0015] Thus, the present invention includes a substrate having a front major surface and a rear major surface, at least one of which comprises: (A) a first high refractive index sheet having a refractive index higher than 1.55 and not including any Ta2O5 layer; (B) a second low refractive index sheet having a refractive index of 1.55 or less and in direct contact with the first sheet; (C) a third high refractive index sheet having a refractive index higher than 1.55 and in direct contact with the former sheet; - a monolayer sublayer having a thickness of 100 nm or more and in direct contact with the former sheet (C), - a multilayer interference coating comprising a stack of at least one high-refractive index layer having a refractive index higher than 1.55 and at least one low-refractive index layer having a refractive index less than or equal to 1.55, is continuously coated with The average reflection coefficient R of 280 nm to 380 nm on the rear principal surface UV weighted by the function W(λ) defined in the ISO 13666:1998 standard, is less than 10% at an incidence angle of 35°. Related to optical lenses.

[0016] The system composed of sheets (A), (B), and (C) and sublayers is used herein as the mechanical and attachment system, and the interference coating is used as the optical system. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The terms "comprise" (and its grammatical variations such as "comprises" and "comprising"), "have" (and its grammatical variations such as "has" and "having"), "contain" (and its grammatical variations such as "contains" and "containing"), and "include" (and its grammatical variations such as "includes" and "including") are open-ended linking verbs. They are used to specify the presence of a stated feature, integer, step, or component, or group thereof, but do not preclude the presence or addition of one or more other features, integers, steps, or components, or groups thereof. As a result, a method or step within a method that "comprises," "has," "contains," or "includes" one or more steps or elements is not limited to having only those one or more steps or elements.

[0018] Unless otherwise indicated, all numbers or expressions referring to quantities of ingredients, ranges, reaction conditions, and so forth used herein are understood to be modified in all instances by the term "about."

[0019] When the optical article includes one or more surface coatings, the phrase "depositing a coating or layer on the optical article" means that the coating or layer is deposited on the outermost coating of the optical article, i.e., the coating closest to the air.

[0020] A coating "on" a surface of a lens is defined as a coating that (a) is disposed above that surface; (b) need not be in contact with that surface, i.e., one or more intervening coatings may be disposed between that surface and the subject coating (but preferably are in contact with the surface); and (c) need not completely cover the surface.

[0021] The term "coating" is understood to mean any layer, layer stack, or film that may be in contact with a substrate and / or with another coating, such as a sol-gel coating or a coating made from an organic resin. Coatings may be deposited or formed by a variety of methods, including wet processes, gaseous processes, and film duplication.

[0022] The term "sheet" is understood to mean a single layer (monolayer) or a bilayer, i.e. a set of two layers that are in direct contact with each other. If a high-index sheet (having a refractive index higher than 1.55) has two layers, both layers are high-index layers. Similarly, if a low-index sheet (having a refractive index lower than 1.55) has two layers, both layers are low-index layers.

[0023] In the present application, a layer based on a material is defined as a layer consisting of at least 80% by weight of said material, more preferably at least 90% by weight of said material, even more preferably a layer of said material, for example a ZrO2-based layer comprises at least 80% by weight of ZrO2.

[0024] The optical article made according to the present invention is a transparent optical article, preferably an optical lens or lens blank, more preferably an ophthalmic lens or lens blank. The optical article may be coated on its convex main surface (front surface), concave main surface (rear surface / back surface), or both surfaces, preferably on the convex (front surface) main surface, with the sheets (A)-(C), sublayers, and multilayer interference coating according to the present invention. As used herein, the back surface of the substrate is intended to mean, in the case of an ophthalmic lens, the surface closest to the wearer's eye when the article is in use. This is generally a concave surface. Conversely, the front surface of the substrate is the surface furthest away from the wearer's eye when the article is in use. This is generally a convex surface. The optical article can also be a planar article.

[0025] As used herein, the term "lens" refers to an organic or inorganic glass lens that includes a lens substrate that may be coated with one or more coatings of various natures.

[0026] The term "ophthalmic lens" is used to mean a lens fitted to a spectacle frame, for example to protect the eye and / or correct vision. Said lens may be chosen from afocal, unifocal, bifocal, trifocal, progressive lenses. Although ophthalmic optics is the preferred field of the invention, it will be understood that the invention can be applied to other types of optical articles, such as lenses for optical instruments in photography or astronomy, optical aiming lenses, ophthalmic visors, optics of lighting systems, etc.

[0027] In this specification, unless otherwise specified, an optical article / material is understood to be transparent if the observation of an image through said optical article is perceived without significant loss of contrast, i.e., the formation of an image through said optical article is obtained without adversely affecting the quality of the image. This definition of the term "transparent" can be applied to all such modified in the description, unless otherwise specified.

[0028] Substrate should be understood in the sense of the present invention as meaning an uncoated substrate and generally has two main faces. Substrate can be an optically transparent material, in particular having the shape of an optical article, for example an ophthalmic lens, which is attached to glass. In this context, the term "substrate" is understood as meaning the base component material of an optical lens, in particular an ophthalmic lens. This material serves as a support for a stack of one or more functional coatings or layers.

[0029] The substrate may be made of inorganic glass or organic glass, preferably organic glass. The organic glass may be any of thermoplastic materials such as polycarbonate and thermoplastic polyurethane, or thermosetting (crosslinked) materials such as diethylene glycol bis(allyl carbonate) polymers and copolymers (especially CR-39® from PPG Industries), thermosetting polyurethanes, polythiourethanes, preferably polythiourethane resins with refractive index of 1.60 or 1.67, polyepoxides, polyepisulfides such as those with refractive index of 1.74, substrates based on poly(meth)acrylates and copolymers, such as substrates containing (meth)acrylic polymers and copolymers derived from bisphenol-A, polythio(meth)acrylates, and copolymers and blends thereof. Suitable materials for the lens substrate are those obtained from polycarbonate (PC), diethylene glycol bis(allyl carbonate) polymers, and thermosetting polythiourethane resins, which are sold by Mitsui Toatsu Chemicals company under the MR series, in particular MR6®, MR7®, and MR8® resins. The latter substrates, as well as the monomers used in their manufacture, are described in particular in U.S. Pat. Nos. 4,689,387, 4,775,733, 5,059,673, 5,087,758, and 5,191,055.

[0030] Prior to depositing the sheets (A)-(C), sub-layers, interference coatings, or other functional coatings, the surface of the article is usually subjected to a physical or chemical surface activation and cleaning pretreatment, such as that disclosed in WO 2013 / 013929, to improve the adhesion of the deposited layers. This pretreatment is usually performed on the surface of an abrasion-resistant and / or scratch-resistant coating (hard coat).

[0031] This pretreatment is usually carried out under vacuum. It can be bombardment with energetic species, for example ion beam methods ("ion precleaning" or "IPC") or electron beam methods, corona treatment, ion spallation treatment, UV treatment, or plasma treatment, typically under vacuum using oxygen or argon plasma. It can also be surface treatment with acids or bases and / or with solvents (using water or organic solvents), with or without ultrasonic treatment. Many treatment methods can be combined. These cleaning treatments optimize the cleanliness of the substrate surface.

[0032] The energy species refers to a species having an energy in the range of 1 to 300 eV, preferably 1 to 150 eV, more preferably 10 to 150 eV, and most preferably 40 to 150 eV. The energy species can be a chemical species such as an ion or a radical, or a species such as a photon or an electron.

[0033] The interference coating may be virtually any interference coating conventionally used in the field of optical systems, in particular ophthalmic optical systems. The interference coating may be, in a non-limiting manner, an anti-reflective coating, a reflective (mirror) coating, such as an infrared mirror or an ultraviolet mirror, a filter in the visible spectrum, such as a blue cut filter or a blue pass filter, but is preferably an anti-reflective coating.

[0034] An antireflective coating is a coating that is deposited on the surface of a product to improve the antireflective properties of the final product. It reduces the reflection of light over a relatively broad portion of the visible spectrum at the product / air interface.

[0035] The multilayer interference coating of the present invention comprises a stack of at least one high refractive index layer, having a refractive index greater than 1.55, and at least one low refractive index layer, having a refractive index less than or equal to 1.55.

[0036] More preferably, it comprises at least two layers with a low refractive index (LI) and at least two layers with a high refractive index (HI). The total number of layers in the interference coating is preferably greater than or equal to 3, more preferably greater than or equal to 4, preferably less than or equal to 8 or 7, more preferably less than or equal to 6, even more preferably less than or equal to 5, most preferably equal to 5 layers.

[0037] As used herein, a layer of an interference coating (or a layer from sheets (A), (B) or (C)) is defined as having a thickness of 1 nm or greater. Thus, when counting the number of layers of an interference coating, layers having a thickness less than 1 nm are not considered. Sublayers and layers of sheets (A)-(C) are not considered when counting the number of layers of an interference coating or when indicating its thickness.

[0038] The HI and LI layers do not necessarily have to alternate with each other in the stack according to one embodiment of the invention, but may. Two HI layers (or more) may be provided on top of each other, and two LI layers (or more) may be provided on top of each other.

[0039] In the present application, a layer of an interference coating is said to be a high refractive index (HI) layer if its refractive index is 1.55 or more, preferably 1.6 or more, more preferably 1.8 or 1.9 or more, most preferably 2 or more. The HI layer preferably has a refractive index of 2.2 or less. A low refractive index layer (LI) is said to be a layer if its refractive index is 1.55 or less, preferably 1.52 or less, more preferably 1.48 or 1.47 or less. The LI layer preferably has a refractive index of 1.1 or more.

[0040] The HI layer typically comprises one or more metal oxides, such as, but not limited to, zirconia (ZrO2), titanium dioxide (TiO2), alumina (Al2O3), tantalum pentoxide (Ta2O5), neodymium oxide (Nd2O5), praseodymium oxide (Pr2O3), praseodymium titanate (PrTiO3), La2O3, Nb2O5, and Y2O3, with the exception that TiO2 is not present in the outermost high refractive index layer of the interference coating. In some aspects of the invention, the outermost high refractive index layer of the interference coating does not comprise titanium oxide. In preferred embodiments, the interference coating does not comprise any layer comprising TiO2, or more generally titanium oxide. In this specification, titanium oxide is intended to mean titanium dioxide or substoichiometric titanium oxide (TiOx, x<2). Titanium oxide-containing layers are indeed subject to photodegradation.

[0041] Optionally, the HI layer may further comprise silica or other materials with a low refractive index, provided that they have a refractive index higher than 1.55, as indicated above. Preferred materials include ZrO2, PrTiO3, Nb2O5, Ta2O5, Y2O3, and mixtures thereof.

[0042] In one embodiment, all high refractive index layers (having a refractive index higher than 1.55) of the interference coating comprise ZrO2. In another embodiment, the interference coating comprises at least one Ta2O5-based layer.

[0043] LI layers are also well known and may include, but are not limited to, SiO2, MgF2, or a mixture of silica and alumina, in particular silica doped with alumina. The latter contributes to increasing the heat resistance of the interference coating. The LI layer is preferably a layer containing at least 80% by weight of silica, more preferably at least 90% by weight of silica, based on the total weight of the layer, and even more preferably consists of a silica layer.

[0044] Optionally, the LI layer may further comprise a high refractive index material, provided that the refractive index of the resulting layer is less than or equal to 1.55.

[0045] The outer layer of the interference coating, i.e., that layer furthest from the substrate, is usually a silica-based layer (e.g. an alumina-doped silica layer) containing at least 80% by weight of silica, more preferably at least 90% by weight of silica, based on the total weight of the layer, and even more preferably consists of a silica layer.

[0046] Typically, the HI and LI layers have a physical thickness in the range of 10 to 120 nm, preferably 20 to 110 nm.

[0047] Generally, the total thickness of the interference coating plus the thickness of the sublayers plus the thickness of the sheets (A) to (C) is less than 1 μm, preferably less than 800 nm, more preferably less than 500 nm, even more preferably less than 450 nm. The total thickness of the interference coating is generally higher than 100 nm, preferably higher than 200 nm, and preferably lower than 1 μm or 500 nm.

[0048] Furthermore, the optical article has good resistance to heat and temperature fluctuations, i.e. high critical temperature. In this patent application, the critical temperature of the article is defined as the initiation temperature at which cracks start to appear in the coating present on the surface of the substrate (on either main face), leading to degradation of the coating (generally an interference coating). The critical temperature of the article coated according to the invention is preferably ≧70° C., more preferably ≧75° C., 80° C., 90° C., 100° C. or 110° C.

[0049] The following R as defined in U.S. Pat. No. 7,692,855: T The following R is slightly different from the ratio T1 It is possible to define ratios.

number

[0050] In the present invention, only the layers of the interference coating have the ratio R T1 , i.e. only layers located above the sublayer are considered for the calculation of

[0051] In one embodiment, R T1 is greater than or equal to 0.8, and preferably greater than or equal to 1, 1.3, 1.5, 1.9, 2, 2.1, 2.2, or 2.5. T1 is less than 5, and preferably less than at least one of the values ​​4, 3.5, and 3. In another embodiment, R T1 In order to obtain an article that exhibits high wear resistance and at the same time a higher critical temperature, a high R T1 It is preferred to have a ratio.

[0052] In the present invention, the multilayer interference coating is deposited on a single sublayer having a thickness of 100 nm or more. It should be noted that such a sublayer does not belong to the interference coating. Said sublayer is preferably in direct contact with the interference coating.

[0053] As used herein, a sub-layer or adhesion layer of an interference coating is intended to mean a relatively thick coating used to improve the mechanical properties, such as the abrasion and / or scratch resistance, of the interference coating and / or to enhance adhesion to the substrate or underlying coating.

[0054] The sublayer generally has a thickness of 600 nm, 500 nm, 450 nm, 400 nm, 375 nm or less, and generally has a thickness of 110 nm or more, more preferably 120, 130, 140, 150, 160, or 180 nm or more. Increasing the thickness of the sublayer improves abrasion resistance.

[0055] The sublayer is preferably a SiO2-based layer, which preferably comprises at least 80% by weight of silica, more preferably at least 90% by weight of silica, relative to the total weight of the layer, and more preferably consists of a silica layer. In another embodiment, the SiO2-based layer is a silica layer doped with alumina in an amount as defined herein above, and preferably consists of a silica layer doped with alumina.

[0056] In the present invention, a single sublayer is deposited on a system of three sheets (A), (B) and (C), which are deposited in this order on an optionally coated substrate. It should be noted that such sheets do not belong to interference coatings. Said sublayer is in direct contact with sheet (C). This system allows improving the wear resistance of optical articles without suffering from adhesion problems between the sublayer and the underlying coating or substrate.

[0057] Indeed, if any measures are taken to improve the wear resistance of the optical article, such as increasing the thickness of the sublayer and / or depositing the sublayer under low pressure in order to increase its compression / density, preferably without additional gas supply, adhesion problems due to mechanical stress may be observed.

[0058] The first high refractive index sheet (A) having a refractive index higher than 1.55 does not include a Ta2O5 layer, and preferably does not include a Ta2O5-based layer. The sheet (A) may include one single high refractive index layer or two high refractive index layers in direct contact. The layers of the sheet (A) generally include one or more metal oxides, which can be selected from the metal oxides mentioned above for the high refractive index layers of the interference coating. Ta2O5 can be present, but preferably in an amount of less than 80% by weight, more preferably less than 75%, 50%, 25%, 10%, 5% or 1% by weight. In one embodiment, the layers of the sheet (A) do not include Ta2O5.

[0059] The sheet (A) preferably comprises a ZrO2-based layer, more preferably is a ZrO2-based layer. In one embodiment, the sheet (A) comprises a ZrO2 layer, more preferably is a ZrO2 layer.

[0060] Sheet (A) preferably has a thickness of 60 nm or less, more preferably 50 nm, 40 nm, 30 nm, 25 nm, 20 nm, or 15 nm or less. Sheet (A) preferably has a thickness of 4 nm or more, more preferably 5 nm or 7 nm or more.

[0061] In one embodiment, the sheet (A) includes a high refractive index silicon organic layer as disclosed in WO 2017 / 021669 pamphlet, which is obtained by vacuum deposition with the assistance of an ion source of at least one metal oxide and at least one organosilicon compound such as octamethylcyclotetrasiloxane, decamethyltetrasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, hexamethyldisiloxane, decamethylcyclopentasiloxane, or dodecylmethylpentasiloxane. The layer includes at least one metal oxide having a refractive index of 1.8 or more such as ZrO2.

[0062] In one embodiment, the sheet (A) includes two directly contacting high refractive index layers, and the high refractive index layer that directly contacts the optionally coated substrate is an adhesion layer. The adhesion layer includes chromium, quasi-stoichiometric silicon oxide SiOx with 0.5 < x < 1.5, preferably 0.9 < x < 1.1, having a refractive index greater than 1.55, and chromium, silicon, and oxygen, preferably a mixture including chromium and silicon oxide, where the silicon oxide represents 50 - 95 wt%, preferably 65 - 92 wt% of the layer, and may include a metal or metal oxide selected therefrom. Examples of commercially available materials that can be used to form the adhesion layer including chromium, silicon, and oxygen are Materials Malbunit8 / 1 (a mixture of SiO2 and Cr) and Flexo (a mixture of SiO and Cr) provided by Umicore Materials AG company. In this embodiment, the adhesion between the sheet (A) and the optionally coated substrate thereunder is improved, and the occurrence of delamination (poor adhesion) is reduced.

[0063] A second low refractive index sheet (B) having a refractive index of 1.55 or less is in direct contact with the sheet (A). The sheet (B) may include one single low refractive index layer or two directly contacting low refractive index layers. The layers of the sheet (B) generally include one or more metal oxides, which can be selected from the metal oxides described above for the low refractive index layers of the interference coating.

[0064] Sheet (B) preferably comprises a SiO2-based layer, more preferably is a SiO2-based layer. In one embodiment, sheet (B) comprises a SiO2 layer, more preferably is a SiO2 layer.

[0065] In one embodiment, sheet (B) comprises a low refractive index silicon organic layer as disclosed in WO 2017 / 021669 obtained by vacuum deposition, with the assistance of an ion source, of at least one organosilicon compound, such as octamethylcyclotetrasiloxane, decamethyltetrasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, hexamethyldisiloxane, decamethylcyclopentasiloxane or dodecamethylpentasiloxane.

[0066] The sheet (B) preferably has a thickness of 80 nm or less, more preferably 75 nm, 70 nm, 65 nm, 60 nm, or 55 nm or less. The sheet (B) preferably has a thickness of 20 nm or more, more preferably 25 nm, 30 nm, or 35 nm or more. In order to improve the abrasion resistance, it is important to make the sheet (B) sufficiently thick.

[0067] When sheet (A) is in direct contact with an uncoated substrate having a refractive index of 1.55 or more, or in direct contact with a coating having a refractive index of 1.55 or more (usually an abrasion-resistant and / or scratch-resistant coating), the thickness of sheet (B) is preferably 60 nm or less or 55 nm or less.

[0068] In one embodiment, the deposition of the layer of sheet (B) is carried out in a vacuum chamber in which no auxiliary gas is supplied during said deposition to increase its densification.

[0069] A third high-refractive index sheet (C), having a refractive index higher than 1.55, is in direct contact with sheet (B). Sheet (C) may include one single high-refractive index layer or two high-refractive index layers in direct contact. The layers of sheet (C) generally include one or more metal oxides, which may be selected from the metal oxides previously described for the high-refractive index layers of the interference coating, such as Ta2O5, Nb2O5, PrTiO3, ZrO2, and Y2O3.

[0070] In one embodiment, sheet (C) does not include a Ta2O5 layer, preferably a Ta2O5-based layer. In another embodiment, Ta2O5 is present in the layer of sheet (C) in an amount of less than 80% by weight, preferably less than 75%, 50%, 25%, 10%, 5%, or 1% by weight. In one embodiment, the layer of sheet (C) does not include Ta2O5.

[0071] Sheet (C) preferably comprises a ZrO2-based layer, more preferably is a ZrO2-based layer. In one embodiment, sheet (C) comprises a ZrO2 layer, more preferably is a ZrO2 layer.

[0072] Sheet (C) preferably has a thickness of 60 nm or less, more preferably 50 nm, 40 nm, 30 nm, 25 nm, 20 nm, or 15 nm or less. In one embodiment, these thickness requirements are met simultaneously by sheets (A) and (C). Sheet (A) preferably has a thickness of 4 nm or more, more preferably 5 nm, 7 nm, or 10 nm or more.

[0073] In one embodiment, the sheet (C) comprises a high refractive index silicon-organic layer as disclosed in WO 2017 / 021669 obtained by vacuum deposition, with the aid of an ion source, of at least one metal oxide and at least one organosilicon compound, such as octamethylcyclotetrasiloxane, decamethyltetrasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, hexamethyldisiloxane, decamethylcyclopentasiloxane or dodecamethylpentasiloxane, said layer comprising at least one metal oxide having a refractive index greater than or equal to 1.8, such as ZrO2.

[0074] The total thickness of the sheets (A), (B) and (C) is preferably in the range of 40 to 100 nm, more preferably 45 to 80 nm or 50 to 75 nm.

[0075] The refractive indices of sheets (A) and (C) can be selected independently from those mentioned above for the high refractive index layers of the interference coating, and the refractive index of sheet (B) can be selected from those mentioned above for the low refractive index layers of the interference coating.

[0076] The total number of layers of the system of sheets (A)-(C) ranges from 3 to 6, more preferably from 3 to 4 or 5, and ideally equal to 3. In other words, sheets (A) and / or (B) and / or (C) are preferably monolayers. The system preferably comprises, in the direction away from the substrate, a ZrO2-based layer, a SiO2-based layer, and a ZrO2-based layer, more preferably a ZrO2-based layer, a SiO2-based layer, and a ZrO2-based layer. The system preferably comprises, in the direction away from the substrate, a ZrO2-layer, a SiO2-layer, and a ZrO2-layer, more preferably a ZrO2-layer, a SiO2-layer, and a ZrO2-layer.

[0077] Optionally, before depositing the first layer of the interference coating, the exposed surface of the sublayer can be subjected to a physical or chemical activation treatment, which can be selected from the pretreatments that can be performed on the substrate before depositing the sublayer already mentioned above. A preferred pretreatment is ion bombardment, for example by using an argon ion beam generated by an ion gun. Such a physical or chemical activation treatment, preferably an ion bombardment treatment, can also be performed on the exposed surface of one or more layers of the multilayer interference coating before depositing a subsequent layer of said multilayer interference coating.

[0078] The optical articles of the present invention can be made antistatic, i.e., not retain and / or generate significant static charge, by incorporating at least one conductive layer in the laminate present on the surface of the article, preferably in an interference coating.

[0079] The ability of a lens to remove the electrostatic charge obtained after generating it by rubbing with a rag or using any other means (charge applied by corona...) can be quantified by measuring the time it takes for said charge to dissipate. Antistatic lenses thus have a discharge time of the order of several hundred milliseconds, preferably less than 500 ms, while for electrostatic lenses this is of the order of several tens of seconds. In the present application, the discharge time is measured according to the method published in patent FR 2 943 798.

[0080] In this specification, "conductive layer" or "antistatic layer" is intended to mean a layer that reduces the ability of the optical article to attract dust / particles due to its presence on the surface of the substrate, due to its charge accumulation.Preferably, when provided on a non-antistatic substrate (i.e., has a discharge time longer than 500 ms), the antistatic layer can be such that the optical article does not retain and / or generate a large amount of static charge, for example, has a discharge time of 500 ms or less after a static charge is applied on its surface, so that small dust particles are prevented from adhering to the optical article by preventing the effect of static electricity.

[0081] The conductive layer can be located at various positions within the stack, typically within or in contact with the interference coating, provided that its reflective or anti-reflective properties are not affected. It is preferably located between two layers of the interference coating and / or is preferably adjacent to the high refractive index layer of such an interference coating. In one embodiment, the conductive layer is located immediately below the low refractive index layer of the interference coating, most preferably it is the penultimate layer of the interference coating by being located immediately below the LI outer layer of the interference coating.

[0082] In one embodiment, the conductive layer is in direct contact with the two layers having a refractive index of 1.55 or less, said conductive layer being preferably located in the penultimate position of the interference coating in the direction away from the substrate.

[0083] The conductive layer should be thin enough so as not to alter the transparency of the interference coating. The conductive layer is preferably made of a conductive and highly transparent material, usually a metal oxide, which may be optionally doped. In this case, its thickness is preferably in the range of 1-15 nm, more preferably 1-10 nm, ideally 2-8 nm. Preferably, the conductive layer comprises an optionally doped metal oxide selected from indium, tin, zinc oxide, and mixtures thereof. Tin-indium oxide (In2O3:Sn, indium oxide doped with tin), zinc oxide doped with aluminum (ZnO:Al), indium oxide (In2O3), and tin oxide (SnO2) are preferred. In the most preferred embodiment, the conductive and optically transparent layer is a tin-indium oxide layer, called an ITO layer or a tin oxide layer.

[0084] Generally, the conductive layer contributes to obtaining interference properties within the stack, but in a limited way due to its small thickness, and typically represents the layer with high refractive index in the coating. This is the case for layers made of conductive and highly transparent materials such as ITO or SnO2 layers. Thus, when present, the conductive layer is preferably the outermost high refractive index layer of the interference coating, or one of the outermost high refractive index layers of the interference coating if it is adjacent to one or more high refractive index layers.

[0085] The conductive layer may be deposited according to any suitable method, for example by vacuum deposition, preferably by ion beam assistance (IAD, described below) to enhance its transparency, or by cathodic sputtering.

[0086] The conductive layer may be a very thin layer of a noble metal (such as Ag, Au, Pt) typically less than 1 nm thick, preferably less than 0.5 nm thick.

[0087] The interference coating, the sublayers and the various layers of the sheets (A) to (C) are preferably deposited by vapor deposition under vacuum according to any of the following methods: i) by evaporation, optionally with ion beam assistance; ii) by ion beam spraying; iii) by cathode sputtering; iv) by plasma-assisted chemical vapor deposition. These various methods are described in the references "Thin Film Processes" and "Thin Film Processes II", edited by Vossen & Kern, Academic Press, 1978 and 1991, respectively. A particularly recommended method is vapor deposition under vacuum. Preferably, the deposition of each of the above-mentioned layers is carried out by vapor deposition under vacuum. Such a process advantageously avoids heating of the substrate, which is particularly interesting for coating substrates that are sensitive to heat, such as organic glasses.

[0088] During the deposition of one or more of the various layers of the interference coating, sublayer or sheets (A) to (C), a treatment step with energetic species as defined above can also be carried out. In particular, working with ion assistance allows packing of said layers while they are being formed, increasing their compressibility and their refractive index. The use of ion assistance during the deposition of a layer produces a layer that is structurally different from the layer deposited without ion assistance.

[0089] Ion-assisted deposition or IAD is described in particular in US Patent Application Publication No. 2006 / 017011 and US Pat. No. 5,268,781. Ion-assisted gas-phase deposition involves depositing a layer of material on a substrate by simultaneously bombarding said layer with an ion beam while it is being formed, preferably under ion bombardment obtained by an ion gun. The ion bombardment causes a rearrangement of atoms in the coating being formed, which increases its density. IAD can not only improve the adhesion of the deposited layers, but also increase their refractive index. The implementation of IAD can be carried out by an ion gun, ions in this case being particles composed of gas atoms, from which one or more electrons are extracted. This preferably consists in bombarding the surface to be treated with oxygen ions. Other ionizing gases can be used, in combination or not with oxygen, for example argon, nitrogen, in particular a mixture of O2 and argon with a volume ratio ranging from 2:1 to 1:2.

[0090] The outermost low refractive index layer of the interference coating is preferably deposited without ion assistance, preferably without concomitant treatment with energetic species. In another embodiment, the low refractive index layer of the interference coating and / or sub-layer is deposited without ion assistance, preferably without concomitant treatment with energetic species.

[0091] In one embodiment, with the exception of the conductive layer (if present in the interference coating), none of the layers of the interference coating are deposited with ion assistance (preferably none of the layers of the interference coating are deposited with concomitant treatment with energetic species).

[0092] In another embodiment, at least one HI layer of the interference coating is deposited under ion assistance, such as a conductive layer or a Ta2O5 layer (if present in the interference coating).

[0093] Optionally, the deposition of one or more of the layers is performed by supplying (auxiliary) gases during the deposition process of the layers in the vacuum chamber, as disclosed in US 2008 / 206470. In particular, additional gases such as noble gases, e.g. argon, krypton, xenon, neon, oxygen, nitrogen, or a mixture of two or more of these gases, are introduced into the vacuum deposition chamber while the layers are being deposited. The gases used during this deposition process are not ionized gases, and more preferably are not activated gases.

[0094] This gas supply allows for the regulation of pressure, which differs from ion bombardment processes such as ion-assisted. This usually makes it possible to limit the stress of the interference coating and to strengthen the adhesion of the layer. When using such a deposition method, called deposition under gas pressure regulation, it is preferable to work under an oxygen atmosphere (so-called "passive oxygen"). The use of an additional gas supply during the deposition of a layer produces a layer that is structurally different from the layer deposited without an additional gas supply.

[0095] In one embodiment of the present invention, the deposition of the sublayers is performed in a vacuum chamber at 1.6×10 -4 Less than mBar, preferably 10 -4 Less than mBar, preferably 8.10 -5 It is carried out under pressure of less than mBar.

[0096] In a preferred embodiment of the invention, the deposition of the sublayer is carried out in a vacuum chamber where no auxiliary gas is supplied during said deposition. It has been found that depositing the sublayer under low pressure, ideally without gas supply to obtain even lower pressures, results in a sublayer with lower porosity, higher compressibility and density, and an increase in the wear resistance of the optical article.

[0097] In another embodiment, the outermost high refractive index layer of the interference coating, except for the conductive layer (if present at the outermost position), is deposited in a vacuum chamber, in which case at least one auxiliary gas is provided during said deposition. In another embodiment, the outermost high refractive index layer of the interference coating, except for the conductive layer (if present at the outermost position), is deposited in a vacuum chamber, in which case at least one auxiliary gas is provided during said deposition.

[0098] According to a particularly preferred embodiment, the optical article comprises, starting from the surface of the substrate, optionally coated with one or more functional coatings, such as a primer coating and / or a hard coat, a high refractive index layer, preferably of zirconia (not a Ta2O5 layer), having a thickness of 3 to 20 nm, more preferably 4 to 14 nm (sheet (A)), a low refractive index layer, preferably of silica, having a thickness of 30 to 65 nm, preferably 35 to 60 nm (sheet (B)), a high refractive index layer, preferably of zirconia, having a thickness of 5 to 25 nm, preferably 6 to 21 nm (sheet (C)), a sublayer, preferably based on silica, having a thickness of 100 to 300 nm, more preferably 110 to 250 nm, even more preferably 120 to 200 nm, and an interference coating, preferably The interference coating preferably comprises an anti-reflection coating, in the following order: a high refractive index layer, preferably of zirconia or Ta2O5, having a thickness of 6-35 nm, preferably 8-30 nm; a low refractive index layer, preferably of silica, having a thickness of 15-50 nm, preferably 18-45 nm; a high refractive index layer, preferably of zirconia or Ta2O5, having a thickness of 20-100 nm, preferably 25-95 nm; optionally a low refractive index layer, preferably of silica, having a thickness of 5-20 nm, preferably 8-15 nm; optionally a conductive layer, preferably of tin oxide or ITO, having a thickness of 3-15 nm, preferably 4-8 nm; and a low refractive index layer, preferably of silica, having a thickness of 60-150 nm, preferably 65-140 nm.

[0099] The interference coating / sublayer / sheet (A)-(C) system can be deposited directly on the bare substrate. In some applications, it is preferred to coat the main surface of the substrate with one or more functional coatings that improve its optical and / or mechanical properties before depositing the interference coating of the present invention. These functional coatings, which are conventionally used in optics, may be, but are not limited to, impact-resistant primer layers, abrasion-resistant and / or scratch-resistant coatings (hard coats), deflection coatings, antistatic coatings, photochromic coatings, colored coatings, or laminates made of two or more of such coatings.

[0100] The impact resistant primer coating that may be used in the present invention may be any coating that is typically used to improve the impact resistance of a finished optical article. By definition, an impact resistant primer coating is a coating that improves the impact resistance of a finished optical article compared to the same optical article but without the impact resistant primer coating.

[0101] Typical impact-resistant primer coatings are (meth)acrylic and polyurethane-based coatings. In particular, the impact-resistant primer coating according to the invention can be prepared from a latex composition such as a poly(meth)acrylic latex, a polyurethane latex, or a polyester latex.

[0102] Preferred primer compositions include thermoplastic polyurethane-based compositions such as those described in JP-A-63-141001 and JP-A-63-87223, poly(meth)acrylic primer compositions such as those described in US Pat. Nos. 5,015,523 and 6,503,631, thermosetting polyurethane-based compositions such as those described in EP-A-0404111, and poly(meth)acrylic or polyurethane latex-based compositions such as those described in US Pat. Nos. 5,316,791 and EP-A-0680492. Preferred primer compositions are polyurethane-based and latex-based compositions, in particular polyurethane latex, poly(meth)acrylic latex, and polyester latex, and combinations thereof. In one embodiment, the impact-resistant primer comprises a colloidal filler.

[0103] Poly(meth)acrylic latexes are latexes based on copolymers made essentially from (meth)acrylates, such as ethyl (meth)acrylate, butyl (meth)acrylate, methoxyethyl (meth)acrylate, or ethoxyethyl (meth)acrylate, typically containing small amounts of at least one other comonomer, such as styrene.

[0104] Commercially available primer compositions suitable for use in the present invention include Witcobond® 232, Witcobond® 234, Witcobond® 240, Witcobond® 242 compositions (available from BAXENDEN CHEMICALS), Neorez® R-962, Neorez® R-972, Neorez® R-986, and Neorez® R-9603 (available from ZENECA RESINS), and Neocryl® A-639 (available from DSM coating resins).

[0105] The thickness of the impact resistant primer coating after curing is typically in the range of 0.05 to 30 μm, preferably 0.2 to 20 μm, more specifically 0.5 to 10 μm, even 0.6 to 5 μm or 0.6 to 3 μm, and most preferably 0.8 to 1.5 μm.

[0106] The impact resistant primer coating is preferably in direct contact with the abrasion and / or scratch resistant coating. In one embodiment, its refractive index is in the range of 1.45 to 1.55. In another embodiment, its refractive index is 1.55 or greater.

[0107] The abrasion- and / or scratch-resistant coating may be any layer conventionally used as an abrasion- and / or scratch-resistant coating in the field of ophthalmic lenses.

[0108] The abrasion-resistant and / or scratch-resistant coating is preferably a hard coating based on poly(meth)acrylates or silanes, which usually contains one or more inorganic fillers intended to increase the hardness and / or refractive index of the coating after curing.

[0109] The abrasion-resistant and / or scratch-resistant coating is preferably made from a composition containing at least one alkoxysilane and / or its hydrolysate, obtained by hydrolysis using, for example, a hydrochloric acid solution and an optional condensation and / or curing catalyst.

[0110] Suitable coatings recommended for the present invention include coatings based on epoxy silane hydrolysates, such as those described in EP 0 614 957, U.S. Pat. No. 4,211,823, and U.S. Pat. No. 5,015,523.

[0111] A preferred abrasion and / or scratch resistant coating composition is that disclosed in EP 0614957 in the name of the applicant. It comprises hydrolysates of epoxytrialkoxysilanes and dialkyldialkoxysilanes, colloidal silica, and a catalytic amount of an aluminum-based curing catalyst such as aluminum acetylacetonate, the remainder consisting essentially of solvents conventionally used to formulate such compositions. Preferably, the hydrolysates used are those of gamma-glycidoxypropyltrimethoxysilane (GLYMO) and dimethyldiethoxysilane (DMDES).

[0112] The abrasion- and / or scratch-resistant coating composition can be deposited by known methods and then cured, preferably using heat or UV radiation. The thickness of the (cured) abrasion- and / or scratch-resistant coating typically varies from 2 to 10 μm, preferably from 3 to 5 μm.

[0113] The optical article according to the invention may also comprise coatings, such as hydrophobic and / or oleophobic coatings (antifouling topcoats), which are formed on the interference coating and can modify its surface properties. These coatings are preferably deposited on the outer layer of the interference coating. Usually, their thickness is less than or equal to 10 nm, preferably in the range of 1 to 10 nm, more preferably 1 to 5 nm. Antifouling topcoats are generally coatings of the fluorosilane or fluorosilazane type, preferably comprising fluoropolyether moieties, more preferably perfluoropolyether moieties. More detailed information on these coatings is disclosed in WO2012076714.

[0114] Instead of a hydrophobic coating, a hydrophilic coating (antifog coating) may be used that imparts antifog properties, or an antifog coating precursor that imparts antifog properties when combined with a surfactant. Examples of such antifog precursor coatings are described in WO 2011 / 080472.

[0115] Additional coatings, such as primers, hard coats, and antifouling top coats, can be deposited on the major surface of the substrate using methods known in the art, such as spin coating, dip coating, spray coating, evaporation, sputtering, chemical vapor deposition, and lamination.

[0116] Typically, the optical article according to the invention comprises a substrate successively coated with an impact-resistant primer layer, an abrasion- and / or scratch-resistant layer, sheets (A)-(C), sublayers, and an interference coating according to the invention, and a hydrophobic and / or oleophobic coating, or a hydrophilic coating imparting anti-fog properties, or an anti-fog precursor coating.

[0117] Due to the presence of the sub-layer and interference coating (anti-reflection coating as an example) according to the invention of sheets (A)-(C), the optical article of the invention exhibits high values ​​of abrasion resistance measured according to the Bayer ASTM (Bayer Sand) operating protocol described below, i.e. according to the ASTM F735-81 standard. For the Bayer ASTM measurement, the coated surface must be a convex surface. In the examples, when the coating is deposited on a concave surface, the Bayer ASTM values ​​are measurements made on the same coating (sheets (A)-(C), sub-layer and interference coating), but deposited on a convex surface.

[0118] According to the invention, an optical article, the main surface of which, preferably the front surface, is covered by the interference laminate of the invention, exhibits a Bayer value (Sand-Bayer value), measured according to the ASTM F735-81 standard, higher than 5.5, preferably higher than any one of 6, 6.5, 7, 7.5, 8, 9, 10, 11. The invention therefore provides an optical article with high abrasion resistance, since a typical Sand-Bayer value for the optical article is about 5. Such a value depends on the thickness of the sublayers and sheets (A) to (C), in particular the sheet (B), R T1 This can be obtained by controlling the ratio and / or the deposition parameters, in particular the pressure during deposition of the sublayers.

[0119] In one embodiment, the optical article is a lens, and the interference coating, sheets (A)-(C), and sublayers are applied on the front major surface of the lens and / or on the back major surface of the lens, preferably on the front major surface of the lens.

[0120] In another embodiment, the optical article is a lens, and the interference coating, sheets (A)-(C) and sublayers are applied on the front main surface (or on the rear main surface) of the lens, and the rear main surface (or the front main surface) of the lens is coated with an interference coating, preferably an anti-reflection coating, which is the same or different from the interference coating on the other surface, optionally with a sublayer which is the same or different from the sublayer on the other surface, optionally with sheets (A)-(C) the same or different from the sheets (A)-(C) on the other surface, and optionally with an impact-resistant primer coating and / or an abrasion-resistant and / or scratch-resistant coating, which is the same or different from those on the other surface. Obviously, the layers on the rear surface are stacked in the same order as the front surface.

[0121] The optical lens of the present invention is designed to reduce reflections in the UVA- and UVB-radiation ranges (315-380 nm and 280-315 nm, respectively) on the rear surface, thus offering optimal health protection against UV rays.

[0122] Spectacle wearers are advised to wear ophthalmic lenses in front of each eye that significantly reduce back surface reflections in the UVA and UVB radiation ranges that are particularly harmful to the retina. Such lenses may also improve visual performance by increasing contrast sensitivity.

[0123] Reflection of UV light is less of a problem on the front surface of the lens, because most of the UV radiation that comes from in front of the wearer and can reach the wearer's eye (normal incidence, 0-15°) is generally absorbed by the substrate of the spectacle lens. On the other hand, if the lens does not have an anti-reflective coating that is effective in the ultraviolet range, UV radiation originating from a source located behind the wearer can be reflected on the back surface of the lens and reach the wearer's eye, thereby potentially affecting the wearer's health. It has been observed that the light rays that can be reflected on the back surface of the lens and reach the wearer's eye have a narrow range of incidence angles, ranging from 30 to 45° (oblique incidence).

[0124] In this regard, the average reflectance R UV weighted by the function W(λ) defined in the ISO 13666:1998 standard is preferably less than 10% or 5%, preferably less than 4.5%, more preferably 4% or less, and even better 3% or less at an angle of incidence of 35°. These performance characteristics can be obtained through the use of an anti-reflective coating deposited on the rear major surface of the lens.

[0125] Average reflectance R of the front principal surface of the substrate from 280 nm to 380 nm UV weighted by the function W(λ) defined in the ISO 13666:1998 standard is preferably higher than 5%, preferably higher than 10% at an angle of incidence of 15°.

[0126] The average reflectance R UV is defined through the following relationship:

number

[0127] The spectral function W(λ) that allows the calculation of the ultraviolet radiation transmission coefficient is defined according to the ISO 13666:1998 standard. It takes into account simultaneously both solar spectral energies Es(λ), where UVB rays are less emitted globally compared to UVA rays, and the spectral efficiency S(λ), where UVB rays are more harmful than UVA rays, and thus allows the user to express the ultraviolet solar radiation distribution moderated by the relative spectral efficiency of such radiation. The values ​​of these three functions in the ultraviolet range are given in a table disclosed in the ISO 13666:1998 standard (reproduced on page 6 of the publication WO 2012 / 076714).

[0128] Ruv is measured in this application at an incidence angle of 35° to the rear principal surface and at an incidence angle of 15° to the front principal surface. Examples of calculations of Ruv for incidence angles at 30° and 45° are given in WO 2012 / 076714. A person skilled in the art can easily perform the calculations based on the reflectance values ​​measured on each surface at the desired incidence angles (15°, 35°).

[0129] The "average light reflectance coefficient" is R v and is also called "luminous reflectance", as defined in the ISO 13666:1998 standard and measured according to the ISO 8980-4 standard (at an angle of incidence less than 17°, typically 15°), i.e. it is the spectral reflectance weighted average over the entire visible spectrum from 380 to 780 nm.

[0130] The average light reflectance R of a lens surface coated with an anti-reflective coating according to the present invention v is preferably 2.5% or less (each side) for each surface of the article, preferably 2% or less, more preferably 1% or less, even more preferably ≦0.85%.

[0131] In each of these embodiments, the total number of layers in the interference coating, preferably the antireflective coating, is preferably 3 or more, preferably 5 or less, and / or the total thickness of the interference coating (preferably the antireflective coating) plus the thickness of the sublayers plus the thickness of sheets (A)-(C) is preferably less than 1 micrometer, more preferably 800 nm or 500 nm or less.

[0132] The colorimetric coefficients C* and h of the optical article of the present invention in the international color system CIE L*a*b* are calculated at 380 to 780 nm, taking into account the standard light source D65 and an observer (incident angle: 15°). The observer is the "standard observer" (10°) defined in the international color system CIE L*a*b*.

[0133] It is possible to prepare interference coatings without any restrictions regarding their hue angle (h), preferably in the range of 40° to 300°, more preferably 50° to 290°, with respect to the residual color displayed by the interference coating (color of reflected light). In some embodiments, the optical article has a hue angle (h) in the range of 240° to 300°, preferably 250° to 290°, more preferably 260° to 280°, so that the perceived residual reflected color is blue to purple, preferably close to purple. In another embodiment, the optical article has a hue angle (h) of 135° or more, more preferably 140° or more, even more preferably in the range of 140° to 160°, thereby obtaining an interference coating with a green reflection. In another embodiment, the optical article has a hue angle (h) in the range of 40° to 90°, preferably 50° to 90°, even more preferably 50° to 70°, so that an interference coating with a gold reflection is obtained.

[0134] In some embodiments of the invention, the interference coating has a chroma (C*) of less than 15 (for an incidence angle of 15°), more preferably less than 13. In the case of ophthalmic lenses, it is preferable from the standpoint of wearer comfort to obtain articles with low residual color intensity (chroma).

[0135] The present invention further relates to a method for producing an optical product as previously described, comprising: - providing an optical lens including a substrate having a front major surface and a rear major surface; - depositing on at least one major surface of the substrate a multilayer interference coating comprising, in this order, a first high-refractive index sheet (A) having a refractive index higher than 1.55 and not including any Ta2O5-layer, a second low-refractive index sheet (B) having a refractive index lower than 1.55 and being brought into direct contact with the former sheet (A), a third high-refractive index sheet (C) having a refractive index higher than 1.55 and being brought into direct contact with the former sheet (B), a single sublayer having an exposed surface and a thickness of 100 nm or more and being brought into direct contact with the former sheet (C), and a stack of at least one high-refractive index layer having a refractive index higher than 1.55 and at least one low-refractive index layer having a refractive index lower than 1.55, thereby obtaining a coated optical product; and an average reflection coefficient R UV weighted by the function W(λ) defined in the ISO 13666:1998 standard is lower than 10% at an incidence angle of 35°.

[0136] In a preferred embodiment, the exposed surface of the sub-layer is subjected to an ion bombardment treatment prior to depositing said multilayer interference coating, and / or deposition of the sub-layer is performed in a vacuum chamber where no auxiliary gas is supplied during said deposition.

[0137] In another embodiment, an exposed surface of at least one layer of the multi-layer interference coating is subjected to an ion bombardment treatment prior to depositing a subsequent layer of said multi-layer interference coating.

[0138] In another embodiment, the exposed surface of each layer of the multilayer interference coating, except for the layer of said coating furthest from the substrate, is subjected to an ion bombardment treatment prior to depositing a subsequent layer of said multilayer interference coating. This embodiment involving bombardment between multiple layers preferably includes a step of bombarding the sublayers under low pressure (<1.6×10 ) to obtain good adhesion of the layers in the interference stack. -4 This is preferably carried out when the material is deposited at 1000 psi (200 psi) or 1000 psi (200 psi) at 100 psi (200 psi) or more preferably in a vacuum chamber without the supply of additional gas during deposition.

[0139] The exposed surface of sheet (C) is preferably subjected to an ion bombardment treatment prior to depositing the subsequent layer, which is a sublayer.

[0140] In another embodiment, the exposed surface of the following layer is subjected to an ion bombardment treatment before depositing the subsequent layer thereon, i.e., sheet (C), the sublayer, and each layer of the multilayer interference coating except for the outermost layer of said coating.

[0141] In one embodiment, the optical article is manufactured by forming a primer coating and / or an abrasion-resistant and / or scratch-resistant coating on a substrate at a first manufacturing location and forming another coating at a second manufacturing location.

[0142] The following examples illustrate the invention in a more detailed but non-limiting manner. Unless otherwise specified, all thicknesses disclosed in this application refer to physical thickness. The percentages given in the tables are weight percentages. Unless otherwise specified, the refractive indexes referred to in this application are expressed at 20-25°C for a wavelength of 550 nm. EXAMPLES

[0143] 1. Basic Procedure The article used in the examples was a polythiourethane MR8® lens substrate (Mitsui Toatsu Chemicals, Ltd.) with a diameter of 65 mm and a spherical power of −2.00 diopters and a thickness of 1.2 mm, the convex surface of which was coated with an impact-resistant primer coating disclosed in the experimental section of WO 2010 / 109154, the refractive index of which was modified to 1.6 by the addition of a high refractive index colloid, an abrasion- and scratch-resistant coating (hard coat) disclosed in Example 3 of EP 0 614 957, the refractive index of which was modified to 1.6 instead of 1.5 by the addition of a high refractive index colloid, and a sheet (A), (B), (C), a sublayer, an anti-reflective coating and an anti-soiling coating disclosed in the experimental section of patent application WO 2010 / 109154, i.e. an anti-soiling coating (thickness: 2-5 nm) by deposition under vacuum of the Optool DSX® compound sold by Daikin Industries. Inc., includes refractive index = 1.59).

[0144] The concave major surface of the substrate was coated with the same impact resistant primer coating and an abrasion and scratch resistant coating (hard coat), as well as an anti-reflective coating to ensure that the concave major surface exhibited an Ruv value of less than 10% at an incidence angle of 35°.

[0145] The various layers, such as the sublayers, sheets (A), (B) and (C), as well as the layer of the anti-reflective coating, were deposited without heating the substrate by vacuum deposition, optionally where specified by oxygen beam and possibly argon ion assisted (IAD) vacuum deposition (evaporation source: electron gun), and optionally where indicated by deposition under pressure control by supplying (passive) O2 gas in the chamber.

[0146] The vacuum deposition equipment making it possible to deposit the various anti-reflection layers was a vacuum coater Syrus 3 from Bulher Leybold Optics having two systems for evaporating the material, an electron gun evaporation system and a thermal evaporator (Joule effect evaporation system), as well as a Mark 2 ion gun from Veeco for use in the preliminary stage of preparation of the substrate surface by argon ion bombardment (IPC) and in the ion-assisted deposition (IAD) of the layers.

[0147] 2. Preparation of Optical Articles The lenses were placed, with the concave side facing the deposition source and ion gun, on a carousel with a circular opening intended to receive the lenses to be processed.

[0148] The method for producing the optical article involves placing the lens substrate with the primer and the abrasion-resistant coating in a vacuum deposition chamber, followed by a pumping step until a high vacuum is created, followed by a conditioning step of the ion gun (IGC as disclosed in French patent no. 2 957 454, starting pressure 3.5×10 -5 mBar, 140V, 3.5A, Argon, 60 seconds) and a starting pressure of 5.10 -4 The process involves a substrate surface activation step (IPC) using bombardment with an argon ion beam at 100 mBar (ion gun set at 1.8 A, 100 V, 60 s), stopping the ion irradiation, followed by sequential deposition of the required number of layers (sheets (A), (B), and (C), sublayers, anti-reflective coating layers, and anti-fouling coatings) at rates ranging from 0.4 to 3 nm / s, and finally a venting step.

[0149] The formation of the anti-reflective laminate according to the present invention is 7.0×10 -5 Depositing a ZrO2 layer (sheet (A)) at a rate of 1 nm / s under an O2 pressure of 10 mBar, depositing a SiO2 layer (sheet (B)) at a rate of 2 nm / s, -5Depositing a ZrO2 layer (sheet (C)) at a rate of 1 nm / s under an O2 pressure of 10 mBar, activating the surface of this ZrO2 layer using an argon ion beam for 30 seconds (the same treatment as the IPC already performed directly on the substrate), and optionally depositing a SiO2 sublayer at a rate of 3 nm / s under an O2 atmosphere (1.6×10 in Example 6 and Comparative Example 2 where O2 gas was supplied). -4 mBar pressure, or 5×10 -5 The process includes the steps of: activating the surface of the sublayer using an argon ion beam for 30 seconds (same treatment as the IPC already performed directly on the substrate), depositing an HI layer (ZrO2 or Ta2O5) at a rate of 2 nm / s, depositing an LI layer (SiO2) at a rate of 2 nm / s, depositing an HI layer (ZrO2 or Ta2O5) at a rate of 2 nm / s, depositing a thin conductive layer (HI, ITO, or SnO2) at a rate of 1 nm / s with oxygen ion assistance (ion gun: 2A, 120V), depositing an LI layer (SiO2) at a rate of 2-3 nm / s, and finally depositing an Optool DSX® layer at a rate of 0.4 nm / s.

[0150] The deposition process of the ZrO2 HI layer was carried out with a gas supply of (O2, 7.5 × 10 -5 The experiment was carried out under a pressure of 10 ...

[0151] The deposition process of the Ta2O5 HI layer was performed using oxygen ion assistance (ion gun: 3 A, 130 V), resulting in a deposition of approximately 2 × 10 -4 This resulted in a pressure of 10 ...

[0152] In Comparative Examples 1 and 2, the sheet (A) was omitted.

[0153] In Comparative Example 8, sheets (A) and (B) were omitted.

[0154] In Comparative Example 9, sheets (A), (B) and (C) were omitted.

[0155] In Comparative Example 10, a sheet (A) was formed using a Ta2O5 material.

[0156] 3. Test Method The following test procedures were used to evaluate the optical articles made according to the present invention: Multiple samples of each system were made for measurement, and the reported data was calculated using an average of the various samples.

[0157] Colorimetric measurements (in reflection) of surfaces coated with the laminates of the invention: the reflection coefficient Rv, the hue angle h, and the chroma C* in the international colorimetric CIE (L*, a*, b*) space were carried out using a Zeiss spectrometer, taking into account the standard illuminant D65 and a standard observer at 10° (for h and C*), and arranged for an angle of incidence of 15°.

[0158] Ruv was calculated from the same reflectance measurements.

[0159] The critical temperature of the article was measured according to the method described in patent application WO 2008 / 001011. The measurement was carried out one month after the article was made.

[0160] The layer thickness was controlled by a quartz crystal microbalance.

[0161] Abrasion resistance was determined as disclosed in WO 2012 / 173596. Specifically, abrasion resistance was measured by Sandbayer test according to ASTM F735-81 standard 24 hours after the manufacture of the article.

[0162] The adhesion properties of the entire interference coating to the substrate were checked on the convex surface of the lens by a test commonly called in French the "n x 10 coups" test (i.e. the "n x 10 blows" test), described in International Patent Applications WO 2010 / 109154 and WO 99 / 49097. The test is carried out in accordance with ISTM02-011. Briefly, the sample to be tested is placed in a clamp and covered with a Celvit cloth saturated with isopropyl alcohol. An eraser placed on a translating holder is brought into contact with the cloth. The eraser is pressed (force = 60 Newtons) against the Celvit cloth placed in contact with the lens. This test consists in determining for each sample the number of cycles required until a defect appears in the anti-reflective coating. Thus, the higher the value obtained in the n x 10 blows test (average of 10 samples), the better the adhesion of the interference coating between the optionally coated substrate, i.e. the sheet (A), and the coating or substrate underneath. An article passed the test if there were no defects after 20 cycles.

[0163] 4.Results The structural characteristics and optical, mechanical and thermomechanical performance of the ophthalmic lens obtained in the examples are detailed below. The sublayer is gray. The total thickness described refers to the thickness of the laminate including the anti-reflective coating and the following additional layers: sublayer, sheet (A), (B) and (C). If not indicated in the table, the laminate is placed on the front main surface of the ophthalmic lens.

[0164] [Table 1]

[0165] [Table 2]

[0166] The optical articles according to the invention having sheets (A), (B) and (C) and sub-layers exhibit better abrasion resistance and better adhesion of the anti-reflective coating than the comparative articles (Example 5 compared with Comparative Example 8 and Example 9), while maintaining a similar level of heat resistance. The Bayer values ​​obtained are generally above 6, indicating a very high level of abrasion resistance.

[0167] It has been observed that suppression of the first high refractive index sheet (A) leads to adhesion problems at the interface with the abrasion and / or scratch resistant coating (data not shown).

[0168] When the first high refractive index sheet (A) and the second low refractive index sheet (B) are suppressed, the abrasion resistance is reduced (compare Example 5 and Comparative Example 8). Furthermore, adhesion problems at the interface with the abrasion-resistant and / or scratch-resistant coating are observed (data not shown).

[0169] When the first high refractive index sheet (A), the second low refractive index sheet (B), and the third high refractive index sheet (C) are suppressed, the abrasion resistance is reduced and poor adhesion to the substrate is observed (compare Example 5 and Comparative Example 9). T1 Increasing the ratio did not restore wear resistance.

[0170] Comparison of Example 3 with Example 4 shows a high R T1 This shows the beneficial effect of having the ratio on wear resistance and critical temperature. A difference of 1.2 points in the Bayer values ​​is obtained, which is highly significant.

[0171] A comparison of Example 5 with Example 4 shows that the use of Ta2O5 instead of ZrO2 in the interference coating results in a slight improvement in the critical temperature. In fact, the critical temperature obtained for the various lenses in Example 4 averages 95°C, and the critical temperature obtained for the various lenses in Example 5 averages 98°C. Both values ​​are rounded to 100°C in the table because critical temperatures are usually given in increments of 10°C. Furthermore, a comparison of Examples 13 and 15 also shows that the use of Ta2O5 instead of ZrO2 in the interference coating results in an improvement in the critical temperature.

[0172] Avoiding the gas supply during deposition of the sublayer improved the abrasion resistance and the critical temperature, but caused adhesion problems in the absence of the sheets (A)-(C) according to the invention (see Comparative Examples 1 and 2). These adhesion problems were not observed in the presence of the sheets (A)-(C) according to the invention when avoiding the gas supply during deposition of the sublayer, and the abrasion resistance and the critical temperature were still improved (compare Example 5 with Example 6).

[0173] Comparison of Example 5 and Comparative Example 10 shows that the use of Ta2O5 instead of ZrO2 in the first high refractive index sheet (A) and / or the third high refractive index sheet (C) should be avoided because this change significantly reduces the abrasion resistance and adhesion properties. Furthermore, the use of ZrO2 in the anti-reflective coating gives slightly better results in terms of abrasion resistance than the use of Ta2O5.

[0174] Examples 13-16 are further examples of optical articles according to the invention having on their respective major concave surfaces another anti-reflective coating that has very low reflectance in the UV range (280-380 nm).

[0175] The concave surface of the optical article of Example 14 was coated with the same primer and hardcoat as the convex surface, and then with the following stack (total thickness: 398 nm): SiO2 (25.7 nm) / ZrO2 (4.7 nm) / SiO2 sublayer (160 nm, oxygen supply during stacking: 1.2×10 -4mBar) / Ta2O5(16.9nm) / SiO2(19.8nm) / Ta2O5(92.2nm) / SnO2(6.5nm) / SiO2(71.2nm) / Anti-fouling coating. On this concave (rear) principal surface, Ruv(35°)=2%.

[0176] For Example 15, Ruv(35°)=2% on the concave (rear) principal surface. For Example 13, Ruv(35°)=2.0% on the concave (rear) principal surface. For Example 16, Ruv(35°)=2.2% on the concave (rear) principal surface. The present disclosure also discloses the following exemplary embodiments. [Embodiment 1] A substrate having a front major surface and a rear major surface, at least one of the major surfaces comprising: - (A) has a refractive index higher than 1.55 and has a Ta 2 O 5 a first high refractive index sheet that does not include any layer; (B) a second low-refractive index sheet having a refractive index of 1.55 or less and in direct contact with said first sheet; (C) a third high refractive index sheet having a refractive index higher than 1.55 and in direct contact with said first sheet; - a monolayer sublayer having a thickness of 100 nm or more and in direct contact with said former sheet (C), - a multilayer interference coating comprising a stack of at least one high-refractive index layer having a refractive index higher than 1.55 and at least one low-refractive index layer having a refractive index less than or equal to 1.55, is continuously coated with The average reflectance R of the rear main surface from 280 nm to 380 nm UV ISO Optical lenses whose reflectance, weighted by the function W(λ) defined in the 13666:1998 standard, is less than 10% at an angle of incidence of 35°. [Embodiment 2] 2. The optical lens of embodiment 1, wherein the sublayer has a thickness greater than 120 nm, preferably greater than 130 nm. [Embodiment 3] 3. The optical lens of embodiment 1 or 2, wherein the deposition of the sublayer is performed in a vacuum chamber where no auxiliary gas is supplied during the deposition. [Embodiment 4] The sublayer is SiO 2 The optical lens according to any one of the first to third embodiments, which is a base layer. [Embodiment 5] The interference coating comprises at least one Ta 2 O 5 5. The optical lens according to any one of the preceding embodiments, comprising a base layer. [Embodiment 6] The interference coating comprises at least one conductive layer, preferably SnO 2 6. The optical lens according to any one of the preceding embodiments, comprising a layer based on [Embodiment 7] 7. The optical lens of any one of the preceding embodiments, wherein the interference coating is an anti-reflective coating. [Embodiment 8] The optical lens according to any one of embodiments 1 to 7, wherein the optical lens is an ophthalmic lens. [Embodiment 9] The first high refractive index sheet (A) having a refractive index higher than 1.55 is made of ZrO 2 The optical lens according to any one of the preceding embodiments, which is a base layer. [Embodiment 10] The second low refractive index sheet (B) having a refractive index of 1.55 or less is made of SiO 2 The optical lens according to any one of the first to nine embodiments, which is a base layer. [Embodiment 11] The third high refractive index sheet (C) having a refractive index higher than 1.55 is Ta 2 O 5 , Nb 2 O 5 , PrTiO 3 , ZrO 2 , and Y 2 O 3 11. The optical lens according to any one of the preceding embodiments, comprising at least one material selected from: [Embodiment 12] The ratio, i.e.

number

Claims

1. a substrate having a front major surface and a rear major surface, at least the rear major surface comprising: - abrasion-resistant and / or scratch-resistant coatings, (A) has a refractive index higher than 1.55, Ta ２ O ５ A first high refractive index sheet that does not include any layer; (B) a second low refractive index sheet having a refractive index of 1.55 or less and in direct contact with said first high refractive index sheet (A); (C) a third high-refractive index sheet having a refractive index higher than 1.55 and in direct contact with said second low-refractive index sheet (B); a single sublayer having a thickness of 100 nm or more and in direct contact with said third high refractive index sheet (C); a multilayer interference coating comprising a stack of at least one high-refractive index layer having a refractive index higher than 1.55 and at least one low-refractive index layer having a refractive index less than or equal to 1.55; is continuously coated with The average reflectance R of the rear principal surface from 280 nm to 380 nm ＵＶ An optical lens, wherein the reflection coefficient W(λ) weighted by the function W(λ) defined in the ISO 13666:1998 standard is less than 10% at an incidence angle of 35°.

2. The optical lens of claim 1 , wherein the sublayer has a thickness of 120 nm or greater.

3. The sublayer is SiO ２ 3. The optical lens according to claim 1, which is a base layer.

4. The interference coating comprises at least one Ta ２ O ５ An optical lens according to any one of claims 1 to 3, comprising a base layer.

5. The optical lens according to any one of claims 1 to 4, wherein the interference coating comprises at least one conductive layer.

6. The interference coating comprises at least one conductive layer of SnO ２ Optical lens according to any one of claims 1 to 5, comprising a layer based on

7. The optical lens according to any one of claims 1 to 6, wherein the interference coating is an anti-reflection coating.

8. The optical lens according to any one of claims 1 to 7, which is an ophthalmic lens.

9. The first high refractive index sheet (A) having a refractive index higher than 1.55 is ZrO ２ The optical lens according to any one of claims 1 to 8, which is a base layer.

10. The second low refractive index sheet (B) having a refractive index of 1.55 or less is made of SiO ２ The optical lens according to any one of claims 1 to 9, which is a base layer.

11. The third high refractive index sheet (C) having a refractive index higher than 1.55 is Ta ２ O ５ , Nb ２ O ５ , PrTiO ３ , ZrO ２ , and Y ２ O ３ 11. The optical lens according to claim 1, comprising at least one material selected from the group consisting of:

12. The ratio, i.e. [0010] The optical lens according to any one of claims 1 to 11, wherein is 0.8 or more.

13. The ratio, i.e. [0025] The optical lens according to any one of claims 1 to 12, wherein is 1.5 or more.

14. The optical lens according to any one of claims 1 to 13, wherein the second low refractive index sheet (B) having a refractive index of 1.55 or less has a thickness of 80 nm or less.

15. The optical lens according to any one of claims 1 to 14, wherein the second low refractive index sheet (B) having a refractive index of 1.55 or less has a thickness of 60 nm or less.

16. The optical lens according to any one of claims 1 to 15, wherein the first high refractive index sheet (A) having a refractive index higher than 1.55 has a thickness of 60 nm or less.

17. The first high refractive index sheet (A) having a refractive index higher than 1.55 and the third high refractive index sheet (C) having a refractive index higher than 1.55 have a thickness of 25 nm or less. The optical lens according to any one of claims 1 to 16.

18. The method for producing an optical lens according to any one of claims 1 to 17, providing an optical lens comprising a substrate having a front major surface and a rear major surface; abrasion-resistant and / or scratch-resistant coating, at least on said rear main surface of said substrate, having a refractive index higher than 1.55 and containing Ta ２ O ５ depositing, in this order, a multilayer interference coating comprising a first high refractive index sheet (A) containing no layers, a second low refractive index sheet (B) having a refractive index of 1.55 or less and adapted to be in direct contact with the first high refractive index sheet (A), a third high refractive index sheet (C) having a refractive index higher than 1.55 and adapted to be in direct contact with the second low refractive index sheet (B), a single sublayer having a thickness of 100 nm or more and adapted to be in direct contact with the third high refractive index sheet (C), and a stack of at least one high refractive index layer having a refractive index higher than 1.55 and at least one low refractive index layer having a refractive index of 1.55 or less; The average reflection coefficient R ＵＶ weighted by the function W(λ) defined in the ISO 13666:1998 standard is less than 10% at an incidence angle of 35°.

19. The method of claim 18, wherein deposition of the sublayer is performed in a vacuum chamber where no auxiliary gas is supplied during deposition.

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