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    • 专利摘要:
    METHOD FOR OBTAINING OPTICAL ITEMS THAT HAVE SUPERIOR ABRASION-RESISTANT PROPERTIES AND COATED ARTICLES PREPARED ACCORDING TO SUCH METHOD This is a method for preparing an abrasion-resistant optical article comprising: providing an optical article that has at least one main face that has an abrasion resistant coating; positioning said optical article in a vacuum deposit chamber; depositing a first inorganic layer comprising SiO2 on said abrasion resistant coating and in direct contact with it by vacuum evaporation of SIO2 and / or SiOx, with 1, in said vacuum chamber, the thickness of said first inorganic layer is in a range of 10 to 100 nm, in which oxygen is introduced into said vacuum chamber during said evaporation; said deposit being conducted without ion assistance; deposit a second inorganic layer comprising SiO2 on said first inorganic layer and in direct contact with it by vacuum evaporation of SiO2 and / or SiOx, with 1 2, in said vacuum chamber, the thickness of said second layer inorganic is in a range of 70 to 300 nm, (...).
    公开号:BR112013032071B1
    申请号:R112013032071-0
    申请日:2011-06-13
    公开日:2020-11-10
    发明作者:Karen West
    申请人:Essilor International；
    IPC主号:
    专利说明:

    BACKGROUND OF THE INVENTION 1. FIELD OF THE INVENTION
    [0001] The present invention relates to a method for the preparation of optical articles that have improved abrasion resistance compared to optical articles of the prior art.
    [0002] The invention also relates to a method for the preparation of abrasion-resistant optical articles that have a top layer that has hydrophilic or hydrophobic properties, leading, in the latter case, to anti-fog articles through an appropriate treatment.
    [0003] The invention also relates to optical articles, especially ophthalmic lenses for glasses obtained through the method of the invention. 2. DESCRIPTION OF RELATED TECHNIQUE
    [0004] The abrasion resistance of optical articles, especially ophthalmic lenses for glasses, has always been a major problem of the technique, especially for organic lenses, whose surfaces are more prone to scratches and abrasion than inorganic lenses.
    [0005] A solution of the technique described in the prior art is to apply a hard inorganic layer on the surface of the organic lens.
    [0006] Document No. JP05173002 describes a double layer system: a very thick first layer (1,500 nm to 2,000 nm) obtained by evaporating SiO under partial pressure of oxygen and deposited in it, a layer of MgF2 or SiO2 , which is not limited in thickness, but whose thickness generally ranges from 80 to 120 nm.
    [0007] The first thick SiO2 layer is formed under a partial pressure of oxygen, typically 2.7x10-2 Pa (2.10-4 torr (2.7 x10'4 mbar)) of oxygen. The partial pressure and deposition rate of this first layer are controlled in such a way that the difference in refractive index between the optical part and the SiO reaction vapor deposition film is within +/- 0.5%. According to document No. JP05173002, the deposition of the second layer prevents reflection.
    [0008] Good resistance to adhesion and abrasion of the film is obtained.
    [0009] The double layer above is deposited directly on the substrate itself (without the conventional hard coating).
    [0010] Document No. US 5,597,622 relates to a process of providing a scratch-resistant coating for a lens made of an organic material (such as made of CR39®). A very thin adhesion layer of SiO is applied first, and is subsequently provided with a thick layer of SiO2.
    [0011] The first layer has a SiO molecule thickness up to 20 nm and, as previously mentioned, is used to improve adhesion.
    [0012] The first layer of SiO is obtained by vaporizing SiO and irradiating the substrate and the SiO layer that is formed with a plasma.
    [0013] A thickness of at least 500 nm for the second layer made of SiO2 is required for wearability. In fact, US Patent No. 5,597,622 discloses that thinner SiO2 layers break even if they are very hard.
    [0014] Numerous patents have revealed the use of abrasion resistant coating compositions that can be defined as hybrid layers, that is, they have organic / inorganic properties. They are usually obtained through hydrolysis and condensation of organic alkoxysilanes, especially epoxialoxysilanes which provide a highly cross-linked matrix.
    [0015] Generally, such coatings also contain a relatively high amount of inorganic fillers such as colloidal metal oxides and / or colloidal silica.
    [0016] Other classically used coatings are (meth) acrylic coatings which can be organic coatings or hybrid coatings, if they contain the same type of fillers described previously.
    [0017] As (met) acrylic coatings are very hard, as such, they are often used without inorganic fillers.
    [0018] The normal thickness of such coatings varies from 1 to 5 microns.
    [0019] The abrasion resistant coatings above can be used in combination with anti-reflective (AR) batteries deposited on them. These AR batteries are generally made of alternating low refractive index and high refractive index inorganic layers, vacuum deposited (physical vapor deposition, chemical vapor deposition (CVD)), optionally under plasma assistance (PECVD).
    [0020] The use of an inorganic sublayer applied between a substrate that has an abrasion resistant coating and an AR stack is known in the art.
    [0021] For example, US No. 2008213473 discloses the use of an SIO2 sublayer interposed between an abrasion resistant coating and an AR battery.
    [0022] According to a main characteristic of the method revealed in document n ° US2008213473, the exposed surface of the sublayer is subjected to an ion bombardment treatment before depositing the AR battery.
    [0023] This treatment is typically conducted under vacuum, using, for example, an argon ion beam generated by means of an ion cannon. Document n ° US2008213473 noted that such a method generally makes it possible on the one hand to improve the abrasion resistance properties of the entire anti-reflective coating and, on the other hand, to increase its adhesion properties, especially the adhesion of the multilayer pile to the sublayer.
    [0024] The sublayer needs to be relatively thick, at least 75 nm, and its thickness generally varies from 75 to 200 nm. US No. 2008213473 describes that the adhesion of the sublayer can be improved by introducing a gas during deposition of the sublayer, such as a rare gas, oxygen or nitrogen.
    [0025] Patent Application W02009004222 describes an ophthalmic lens that has an AR cell deposited in a SYO2 sublayer comprising two layers in which a first layer is deposited without ion assistance and the second layer of said sublayer is deposited with assistance from ion.
    [0026] The AR cells above comprise, in addition to the inorganic sublayer (which can itself be a composite sublayer that has multiple layers), at least 4 layers of mineral that involve different materials that have different internal forces and mechanical properties AR that includes abrasion resistance and adhesion are the result of a subtle balance between the layers that are under tension or compression force.
    [0027] Generally, the consequence of depositing multiple inorganic layers in an abrasion resistant coating is to weaken the entire pile, especially if a high number of inorganic layers is deposited in an abrasion resistant coating.
    [0028] There is still a need in the art to obtain coatings that have high abrasion resistant properties that are simple to prepare, and which are not used in combination with anti-reflective coatings, especially inorganic anti-reflective coatings.
    [0029] Numerous patents have proposed technical solutions to improve the abrasion-resistant properties of the abrasion-resistant coating by trying to modify the intrinsic properties of such coatings, for example, in the case of abrasion-resistant sun / gel coatings, using precursors that increase the degree of crosslinking of the abrasion resistant coating matrix or using specific catalytic curing systems.
    [0030] A first goal of this invention is to provide an optical article that has improved abrasion resistant properties compared to the prior art.
    [0031] Another goal of this invention is to provide an optical article that has improved abrasion resistance starting from an optical article already coated with an abrasion resistant coating without intrinsically modifying that abrasion resistant coating. SUMMARY OF THE INVENTION
    [0032] Therefore, a first objective of the invention is to provide a process for obtaining an abrasion-resistant optical article that has improved abrasion resistance.
    [0033] Especially, the process used to obtain abrasion resistant optical articles is simple and can be applied to any article already coated with an abrasion resistant coating.
    [0034] To achieve the aforementioned objectives, a process is provided for the preparation of an abrasion resistant optical article comprising: a) providing an optical article that has at least one main face that has an abrasion resistant coating; b) positioning said optical article in a vacuum deposition chamber; c) deposit a first inorganic layer comprising SiO2 for and in direct contact with said abrasion resistant coating through evaporation of SiO2 and / or SiOx, with 1 <x <2 under vacuum in said vacuum chamber, the thickness being said first inorganic layer varies from 10 to 30 nm, in which oxygen is introduced into said vacuum chamber during said evaporation; said deposition being conducted without ion assistance; d) deposit a second inorganic layer comprising SiO2 to and in direct contact with said first inorganic layer through evaporation of SiO2 and / or SiOx, with 1 <x <2 under vacuum in said vacuum chamber, the thickness of which said second inorganic layer varies from 70 to 150 nm, in which said deposition is conducted without ion assistance, the pressure during the deposition of said second inorganic layer being lower than the pressure during the evaporation of said first inorganic layer and, optionally; e) apply, to and in direct contact with said second inorganic layer, a hydrophobic or hydrophilic layer that has a thickness ranging from 1 to 15 nm.
    [0035] According to the invention, the second inorganic layer will be the most peripheral layer of the pile, that is, the layer in contact with air if no additional layer is applied in step e).
    [0036] If step e) is implanted, the additional layer (hydrophilic or hydrophobic) will become the most peripheral layer of the pile, in contact with air.
    [0037] The invention also relates to articles that have abrasion resistant coatings obtained through the process of the invention.
    [0038] Other objectives, resources and advantages of the present invention will become evident from the detailed description below. It should be understood, however, that the detailed description and the specific examples, although indicating the specific modalities of the invention, are given only by way of illustration, since various changes and modifications within the spirit and scope of the invention will become evident to those versed in technique from that detailed description. DETAILED DESCRIPTION OF THE INVENTION AND PREFERENTIAL MODALITIES
    [0039] The terms "comprises" (and any grammatical variation thereof, such as "comprise" and "comprising"), "has" (and any grammatical variation thereof, such as "have" and "having"), " contains "(and any grammatical variation thereof, such as" contain "and" containing "), and" includes "(and any grammatical variation thereof, such as" include "and" including ") are open link verbs. They are used to specify the presence of resources, whole numbers, steps or components or groups indicated therein, but do not exclude the presence or addition of one or more other resources, whole numbers, steps or components or groups thereof. As a result, a method, or a step in a method, that "comprises", "has", "contains" or "includes" one or more steps or elements has that one or more steps or elements, but is not limited to having only that one or more steps or elements.
    [0040] Unless otherwise stated, all numbers or expressions that refer to the quantities of ingredients, ranges, reaction conditions, etc. used in this document are to be understood as modified in all examples by the term "approximately".
    [0041] When the optical article comprises one or more surface coatings, the term "deposit a layer on the optical article" means that a layer is deposited on the most peripheral coating of the optical article.
    [0042] The outer layer in a coating pile is the layer that is closest to the air, before the deposition of other coating (s).
    [0043] A layer is said to be in direct contact with another layer when 1) no interlayer is present between the two layers, or 2) only a very thin layer, that is, less than 5 nm in thickness, preferably less than 2 nm thick, is interspersed between the two layers.
    [0044] The preferred meaning of direct contact is that there is no layer interspersed between the two respective layers.
    [0045] In the context of the invention, an inorganic layer should be understood as a layer that contains less than 5% by weight of carbon, preferably less than 2% by weight of carbon, preferably less than 1% and, so ideal, contains no carbon.
    [0046] The optical article that has an abrasion resistant coating is preferably a lens, more preferably an ophthalmic lens or lens plate for glasses.
    [0047] In this document, the term "lens" means an organic or inorganic glass lens, preferably an organic lens that comprises a lens substrate that can be coated with one or more coatings of various natures.
    [0048] The method of the invention can be used for the manufacture of coated optical articles on the main convex side (front side), on the main concave side (rear side), or on both sides thereof.
    [0049] As used in this document, the concave face or "back face" or rear side of the optical article means the face that is located closest to the user's eye. On the contrary, the "front face" (typically convex) of the substrate, means the face that, in the final article, is the furthest from the user's eye.
    [0050] According to the method of the invention, an optical article that already has an abrasion resistant coating is supplied first.
    [0051] By definition, an abrasion resistant coating is a coating that improves the abrasion resistance of the optical article compared to the same optical article, but without the abrasion resistant coating.
    [0052] The abrasion resistant coating composition composition can be a heat-curable and / or UV composition.
    [0053] In a preferred embodiment of the present invention, the abrasion resistant coating of the optical article is a sol-gel coating. The term "sol-gel" refers to materials that undergo a series of reactions, including hydrolysis and condensation and undergo the transition from sun to gel. Typically, a metallic compound, such as a metal alkoxide or metal salt, hydrolyzes to form a metal hydroxide. The metal hydroxides then condense in solution to form a hybrid organic / inorganic polymer. Under certain conditions, these polymers condense to form a networked gel.
    [0054] The preferred abrasion-resistant sol-gel coatings are silicon-based coatings, which can be obtained by curing a precursor composition containing silanes or hydrolysates thereof. The silicon sol-gel coating compositions of the present invention are homogeneous mixtures of a solvent, a silane and / or an organosilane and, optionally, a catalyst which are processed to form a coating suitable for optical application. The term "homogeneous", as used herein, refers to a form that has a similar or completely uniform structure and is given the common meaning known to persons skilled in the art.
    [0055] In a preferred embodiment of the invention, the abrasion-resistant curable coating composition comprises at least one compound of the formula:

    [0056] or a hydrolyzate thereof, in which the R groups are identical or different and represent monovalent organic groups attached to the silicon atom through a carbon atom, the X groups are identical or different and represent hydrolyzable groups and n is a number integer equal to 1 or 2.
    [0057] The organosilanes of formula I have two or three X groups linked directly to the silicon atom, each of which leads to an OH group through hydrolysis and one or two monovalent organic R groups linked to the silicon atom. It should be noted that SiOH bonds may be present initially in the compounds of formula I, which are considered in this case as hydrolysates. Hydrolysates also include siloxane salts.
    [0058] Groups X may independently represent and without limitation alkoxy groups -O-R1, where R1 preferably represents a branched or linear alkoxyalkyl or alkyl group, preferably a C1-C4 alkyl group, acyloxy groups -OC (O) R3, wherein R3 preferably represents an alkyl group, preferably a C1-C6 alkyl group, and more preferably an ethyl or methyl group, halogen groups such as Cl and Br, amino groups optionally substituted with one or two functional groups such as a silane group or alkyl, for example, the NHSiMes group, alkylenoxy groups such as the isopropenoxy group.
    [0059] Groups X are preferably alkoxy groups, in particular methoxy, ethoxy, propoxy or butoxy, more preferably methoxy or ethoxy. In that case, the compounds of formula I are alkoxysilanes.
    [0060] In one embodiment of the invention, the silanes of formula I have at least one group R that contains at least one polymerizable function. Such silanes include, but are not limited to, epoxysilanes, unsaturated organosilanes such as allylsilanes, acrylic vinyl silanes, methacrylic silanes, preferably comprising a terminal ethylene double bond.
    [0061] Among the compounds of formula I, a preferred class of compounds includes compounds of formula:

    [0062] or hydrolysates thereof, where the R groups are identical or different and represent the monovalent organic groups attached to the silicon atom through a carbon atom, the Y groups are identical or different and represent the monovalent organic groups attached to the silicon atom through a carbon atom and containing at least one epoxy function, groups X are identical or different and represent hydrolyzable groups, men 'are integers so that m is equal to 1 or 2 and n' + m = 1 or 2.
    [0063] Whole numbers do not even define three groups of compounds II: compounds of formula RYSi (X) 2, compounds of formula Y2Si (X) 2 and compounds of formula YSi (X) s. Among these compounds, epoxysilanes that have the formula YSi (X) 3 are preferred.
    [0064] The monovalent R groups linked to the silicon atom through a Si-C bond are organic groups. Such groups can be, without limitation, hydrocarbon groups, saturated or unsaturated, preferably C1-C10 groups and preferably C1-C4 groups, for example, an alkyl group, preferably a C1-C4 alkyl group such as methyl or ethyl, a group aminoalkyl, an alkenyl group, such as a vinyl group, a CΘ-CW aryl group, for example, an optionally substituted phenyl group, in particular a phenyl group substituted with one or more C1-C4 alkyl groups, a benzyl group, a group (met) acryloxyalkyl.
    [0065] The most preferred R groups are alkyl groups, in particular C1-C4 alkyl groups and, ideally, methyl groups.
    [0066] The monovalent Y groups linked to the silicon atom through a Si-C bond are organic groups since they contain at least one epoxy function, preferably an epoxy function. Epoxy function means a group of atoms, in which an oxygen atom is directly linked to two adjacent carbon atoms or non-adjacent carbon atoms comprised in a carbon-containing chain or a system containing cyclic carbon. Among the epoxy functions, oxirane functions are preferred, that is, cyclic ether groups with three saturated members.
    [0067] The preferred Y groups are groups of formulas III and IV:

    [0068] where R2 is an alkyl group, preferably a methyl group, or a hydrogen atom, ideally a hydrogen atom, a and c are integers ranging from 1 to 6, and b is 0, 1 or 2.
    [0069] The preferred group having formula III is the y-glycidoxypropyl group (R2 = H, a = 3, b = 0) and the preferred (3,4-epoxycyclohexyl) alkyl group of formula IV is the β- (3,4-epoxycyclohexyl) ethyl (c = 1). The y-glycidoxyethoxypropyl group can also be used (R2 = H, a = 3, b = 1).
    [0070] The preferred epoxysilanes of formula II are epoxy alkoxysilanes, and more preferred are those having one group Y and three groups X alkoxy. Particularly preferred epoxytrialoxysilanes are those of formulas V and VI: V

    [0071] where R1 is preferably a methyl or ethyl group, and a, b and c are as defined above.
    [0072] Examples of such epoxysilanes include, but are not limited to, y-glycidoxy methyl trimethoxysilane, y-glycidoxy methyl triethoxysilane, y-glycidoxy methyl tripropoxysilane, y-glycidoxy ethyl trimethoxysilane, y-glycidoxy ethyl triethoxylane, y-glycidoxy ethylethoxy y-glycidoxy ethyl triethoxysilane, Y-glycidoxy ethyl tripropoxysilane, y-glycidoxy propyl trimethoxysilane, y-glycidoxy propyl triethoxysilane, y-glycidoxy propyl tripropoxysilane, y-glycidoxy propyl trimethoxysilane, y-glycidoxy propyl triethoxysilane, y-glycoside glycidoxy propyl trimethoxysilane, y-glycidoxy propyl triethoxysilane, y-glycidoxy propyl tripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane. Other useful epoxytrialoxysilanes are described in US Patents 4,294,950, US 4,211,823, US 5,015,523, EP 0614957 and WO 94/10230, which are incorporated herein by reference. Among those silanes, y-glycidoxypropyltrimethoxysilane (GLYMO) is preferred.
    [0073] The content of the theoretical dry extract of compound I in the abrasion resistant coating composition is generally variable from 20 to 80%, preferably 25 to 60% by weight, based on the total weight of the theoretical dry extract.
    [0074] The theoretical dry weight of a composition is defined as the sum of the theoretical dry weight of each of its components. As used herein, the theoretical dry weight of compounds of formula I or II is the weight calculated in units RnSi (O) (4-n) / 2 or RnYmSi (O) (4.n'-m) / 2, where R, Y, n, n 'em are as previously defined.
    [0075] The presence of an epoxy alkoxysilane is preferred in the composition of the abrasion resistant coating. It provides a highly cross-linked matrix.
    [0076] In some embodiments, the hard coating composition comprises fillers, usually nanoparticles (or nanocrystals), to increase the hardness and / or the refractive index of the cured coating. Nanoparticles can be organic or inorganic. A mixture of both can also be used. Preferably, inorganic nanoparticles are used, especially metalloid or metallic oxide.
    [0077] "Nanoparticles" means particles whose diameter (or longest dimension) is less than 1 pm, preferably less than 150 nm and even more preferably less than 100 nm. In the present invention, the fillers or nanoparticles preferably have a diameter ranging from 2 to 100 nm, more preferably from 2 to 50 nm, and even more preferably from 5 to 50 nm.
    [0078] Suitable inorganic nanoparticles are, for example, aluminum oxide nanoparticles AI2O3, silicon oxide SiO2, zirconium oxide ZrO2, titanium oxide T2O, antimony oxide Sb2θs, tantalum oxide Ta2θ5, oxide oxide, oxide oxide tin Snθ2, indium oxide, cerium oxide, SYNN4, or mixtures thereof.
    [0079] It is also possible to use particles of composite particles or mixed oxides, for example, those that have a layer / core structure. The use of different types of nanoparticles allows to make nanoparticles layers with heterostructure.
    [0080] Preferably, the nanoparticles are particles of aluminum oxide, tin oxide, zirconium oxide or silicon oxide SiO2, more preferably nanoparticles of SiO2. Mineral fillers are preferably used in colloidal form, that is, in the form of fine particles dispersed in a dispersion medium such as water, an alcohol, a ketone, an ester or mixtures thereof, preferably an alcohol.
    [0081] The curable composition of the invention optionally comprises a catalytic amount of at least one curing catalyst, in order to accelerate the curing step.
    [0082] Examples of curing catalysts are aluminum acetylacetonate, metal carboxylates such as zinc, titanium, zirconium, tin or magnesium.
    [0083] Condensation catalysts such as acid anhydrides or unsaturated or saturated polyfunctional acids can also be used, in particular maleic acid, itaconic acid, trimellitic acid or trimellitic anhydride. Numerous examples of condensation and / or curing catalysts are given in "Chemistry and Technology of the Epoxy Resins", B. Ellis (Ed.) Chapman Hall, New York, 1993 and "Epoxy Resins Chemistry and Technology" 2nd edition, CA May (Ed.), Marcel Dekker, New York, 1988.
    [0084] In another embodiment, the abrasion resistant coating can be a (meth) acrylate based coating, which is typically UV-curable. The term (meth) acrylate means methacrylate or acrylate. The coating can be obtained especially from a mixture of an acrylate and an epoxy monomer. Useful polyepoxy monomers are disclosed, for example, in document No. US2007 / 0275171 and US 6,984,262, which are incorporated by reference in this document.
    [0085] The main component of the curable coating composition based on (meth) acrylate can be chosen from monofunctional (meth) acrylates and multifunctional (meth) acrylates such as bifunctional (meth) acrylates; (meth) trifunctional acrylates; (meth) tetrafunctional acrylates, (meth) pentafunctional acrylates, (meth) hexafunctional acrylates.
    [0086] Examples of monomers that can be used as main components of (meth) acrylate based coating compositions are: - moπofuπcioπal (meth) acrylates: alii methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, caprolactacyl acrylate, isobornyl methacrylate, lauryl methacrylate, polypropylene glycol monomethacrylate. - Bifunctional (meth) acrylates: 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, bisphenol A ethoxylated diacrylate, polyethylene glycol di (meth) acrylates such as diacrylate polyethylene glycol, tetraethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol dimethacrylate, diethylene glycol diacrylate. - Trifunctional (meth) acrylates: Trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate. - tetra to hexa (meth) acrylates: dipentaerythritol pentacrylate, pentaerythritol tetracrylate, ethoxylated pentaerythritol tetracrylate, pentacrylate esters.
    [0087] The abrasion resistant coating composition can be deposited on at least part of a main face of the substrate of the optical article, preferably on all said main face, using any of the methods used in coating technology such as, for example, example, spray coating, rotation coating, flow coating brush coating, dip coating or roller coating. Spin coating and dip coating are the preferred methods. The composition can also be applied by a series of successive layers or thin coatings on the substrate to achieve the desired thickness.
    [0088] It is then cured by conventional technique (for example, thermal or UV).
    [0089] Abrasion resistant coatings have a thickness that preferably ranges from 1 to 10 pm, more preferably from 2 to 5 pm, even more preferably 3 to 5 pm.
    [0090] The substrate can be made of mineral glass or organic glass, preferably organic glass (polymer substrate). Organic glasses can be made from any material currently used for organic ophthalmic lenses, for example, thermoplastic materials such as thermoplastic polycarbonates and polyurethanes or thermosetting (crosslinked) materials, such as those obtained by polymerizing ally derivatives, such as carbonates of aliphatic linear or branched aromatic or aliphatic polyols, such as diethylene glycol bis (allyl carbonate), isopropylene bisphenol-A bis (allyl carbonate), poly (meth) acrylates and copolymer-based substrates, polythio (meth) acrylates , thermosetting polyurethanes, polythiourethanes, polyepoxides, poliepisulfides, as well as copolymers and mixtures thereof.
    [0091] Particularly recommended substrates are polycarbonates, for example, those made of bisphenol-A polycarbonate, marketed, for example, under the trademarks LEXAN® with General Electric or MAKROLON® with Bayer AG, or those that incorporate groups functional polycarbonate, in particular substrates obtained by polymerization or copolymerization of diethylene glycol bis (allyl carbonate), marketed under the trademark CR-39® with PPG INDUSTRIES. By (meth) acrylate, an acrylate or methacrylate group is represented.
    [0092] Optionally, the substrate is coated with an impact resistant primer coating. The impact resistant initiator coating that can be used in the present invention can be any coating typically used to improve the impact resistance of a finished optical article. Furthermore, this coating generally enhances the adhesion, if present, of the abrasion resistant coating of the invention to the substrate of the finished optical article. By definition, an impact resistant initiator coating is a coating that improves the impact resistance of the finished optical article as compared to the same optical article, but without the impact resistant initiator coating.
    [0093] The typical impact resistance initiator coatings are (met) acrylic based coatings and polyurethane based coatings. Impact resistant coatings based on (meth) acrylic are, among others, disclosed in patent documents No. US 5,015,523 and US No. 6,503,631 while thermoplastic and polyurethane resin coatings of cross-linked basis are disclosed among others, in patent documents No. JP 63-141001 and No. JP 63-87223, patent document No. EP 0404111 and patent document No. US 5,316,791.
    [0094] In particular, the impact resistant primer coating according to the invention can be made of a latex composition, such as a poly (meth) acrylic latex, a polyurethane latex or a polyester latex.
    [0095] Preferably, the impact resistant primer coating has a glass transition temperature (Tg) of less than 30 ° C. Among the preferred compositions of impact resistant primer coatings, acrylic latex sold under the brand Acrylic latex A-639 with Zeneca and polyurethane latexes sold under the brands W-240 and W-234 with Baxenden Chemicals or Witcobond .
    [0096] The impact resistant primer coating composition can be simply dried or optionally pre-cured before molding the optical substrate.
    [0097] The thickness of the impact resistant primer coating, after curing, typically ranges from 0.05 to 30 pm, preferably 0.5 to 20 pm and more particularly from 0.6 to 15 pm, and even more preferably from 0 , 6 to 5 pm and most preferably 0.6 to 1.2 microns.
    [0098] According to the invention, the optical article that has an abrasion resistant coating is positioned in a vacuum chamber.
    [0099] Optionally, the surface of the article that has the abrasion resistant coating to which the first inorganic layer is deposited can be subjected to a chemical or physical pre-treatment step to improve adhesion, for example, a plasma treatment high frequency discharge, a luminescent discharge plasma treatment, a Corona treatment, an electron beam treatment, an ion beam treatment (IPC: ion pre-cleaning), a solvent treatment or an acid treatment or base (NaOH).
    [0100] Preferably, an IPC Treatment is implemented.
    [0101] Then, the first inorganic layer is applied by depositing a layer of SiO2 in the resistant coating and in direct contact with it to the abrasion by evaporating SiO2 and / or SiOx, preferably SiO2, with 1 <x <2 under vacuum in said chamber. vacuum, the thickness of said first inorganic layer varying from 10 to 100 nm, more preferably from 10 to 50 nm, more preferably from 10 to 30 nm.
    [0102] Oxygen gas (O2) is introduced into said vacuum chamber during said evaporation; said deposition being conducted without ion assistance. This gas supply, which makes it possible to increase the pressure, diverges from an IAD (ion-assisted deposition) treatment, in which the layer does not undergo a bombardment of activated species such as with ions.
    [0103] During the first stage of deposition of the method of the invention, there is no bombardment of the first inorganic layer by energetic species, as created by a plasma treatment, a Corona type treatment or an ion cannon.
    [0104] As used herein, "energetic species" are species defined as having an energy range of 1 to 150 eV, preferably 10 to 150 eV, and more preferably 40 to 150 eV. Energetic species can be chemical species such as ions, radicals or electron-like species.
    [0105] Preferably, the pressure during the deposition of the first layer of SiO2 layer is greater than or equal to 1 x 10'2 Pa (1x10'4 mbar) and varies most preferably from 1.2 x 10-2 to 5 x 10- 2 Pa (1.2x10-4 mbar at 5 x 10-4 mbar).
    [0106] Without limiting the theory, the inventors believe that by increasing the gas pressure by introducing oxygen into the vacuum chamber, the molecules in the first formed inorganic layer are more widely spaced from each other, thus resulting in a layer that has a low level of density.
    [0107] The deposition rate during the deposition of the first layer preferably ranges from 0.2 to 0.5 nm / s.
    [0108] The first inorganic layer comprising SiO2 comprises at least 80% by weight of SiO2, preferably at least 90% by weight of SiO2, more preferably at least 95% by weight and even more preferably 100% by weight of SiO2.
    [0109] Before applying the second layer of the invention, a surface activation treatment of the first inorganic layer can be implanted, for the purpose of improving adhesion, such as ion beam treatment, Corona treatment or plasma treatment or an acidic or basic treatment.
    [0110] In a preferred modality, in the activation treatment it is implanted before depositing the second inorganic layer and, in addition, there is no layer interspersed between the first and the second inorganic layer.
    [0111] Then, a second inorganic layer comprising SiO2 is deposited into and in direct contact with said first inorganic layer through vacuum evaporation of SiO2 and / or SiOx, with 1 <x <2, preferably SiO2, in the vacuum, the thickness of said second inorganic layer varying from 70 to 300 nm, preferably from 70 to 200 nm, more preferably from 70 to 150 nm, even more preferably from 70 to 100 nm, without the introduction into the vacuum chamber of an additional gas such as oxygen gas, nitrogen gas, or inert gas such as rare gas and no treatment step step (especially no ion assistance) with energetic species of the second inorganic layer comprising SiO2 is conducted during the deposition thereof.
    [0112] The pressure inside said vacuum chamber during the deposition of said second inorganic layer is lower than the pressure during the previous deposition step.
    [0113] Preferably, the pressure inside said vacuum chamber during the deposition of the second inorganic layer ranges from 0.2 x 10-2 to 0.5 x 10'2 Pa (0.2 x 10'4 to 0, 5 x 10'4 mbar).
    [0114] The deposit rate during deposit of the second layer is preferably in the range of 0.7 to 1.3 nm / s.
    [0115] In the two previously described deposit methods of the second inorganic layer comprising SiO2, the resulting layer will have a density greater than the density of the first inorganic layer.
    [0116] The second inorganic layer comprising SiO2 comprises at least 80% by weight of SiO2, preferably at least 90% by weight of SiO2, more preferably at least 95% by weight and even better 100% by weight of SiO2.
    [0117] If no other layer is applied to said second inorganic layer, that second inorganic layer becomes the upper (outer) layer of the entire deposited cell and is then in direct contact with air.
    [0118] At this stage, the optical article thus coated has an improved abrasion resistance compared to the abrasion resistance of the initially coated optical article.
    [0119] In an additional optional step of the method of the invention, a hydrophilic layer or a hydrophobic layer that preferably has a thickness that is in a range of 1 to 15 nm is applied over the second inorganic layer and in direct contact with it and it becomes the outermost layer of the entire pile, in contact with air.
    [0120] The mode in which the outermost layer is a hydrophilic layer will now be described in more detail.
    [0121] In the context of the invention, a hydrophilic layer is a layer that has a static water contact angle of less than 50 °.
    [0122] Preferably, the hydrophilic layer has a static water contact angle less than 45 °, more preferably <40 °, even better <30 ° and ideally <25 °.
    [0123] According to a first embodiment, a hydrophilic layer is deposited on the second inorganic layer and in direct contact with it by the permanent graft of at least one organosilane compound that has: - at least one polyoxyalkylene group which preferably comprises less than 80 carbon atoms, and - at least one Si atom that has at least one hydrolyzable group.
    [0124] This hydrophilic layer can act as a precursor layer to an anti-fog coating.
    [0125] In the context of the invention, a "precursor layer of an anti-fog coating" is a coating that acquires anti-fog properties when an appropriate liquid surfactant is applied to it and is absorbed on its surface.
    [0126] Preferably, the precursor layer of the anti-fog coating is less than 5 nm thick, more preferably less than 4 nm and even better less than 3 nm and exhibits a static contact angle with water generally greater than 10 ° and less than 50 °.
    [0127] Such a hydrophilic layer can be deposited in liquid form by a classic deposit method (dip or spin coating) or under vacuum, preferably by evaporation under vacuum.
    [0128] If the hydrophilic layer is deposited in liquid form, it is recommended to avoid condensation of hydrolysed organosilane compounds so that they maintain a maximum of free silanol groups in order to facilitate the grafting of such compounds on the surface of the optical article.
    [0129] The organosilane compound can, due to its reactive group containing silicon, create a covalent bond with the silanol groups on the surface of the second inorganic layer.
    [0130] The preferred organosilane compound used to obtain the hydrophilic layer comprises a polyoxyalkylene chain functionalized at one or two of its terminal ends, preferably only at one end, by a group comprising at least one of one Si atom it has at least one hydrolyzable group.
    [0131] This organosilane compound preferably comprises an Si atom that has at least two, preferably three hydrolyzable groups.
    [0132] Preferably, it does not comprise urethane groups.
    [0133] Preferably, the organosilane compound has the following formula:

    [0134] wherein Y groups, identical or different, are organic monovalent groups linked to silicon by a carbon atom. Groups X, identical or different, are hydrolyzable groups; R1 is m group that comprises a polyoxyalkylene function, m is an integer equal to 0, 1 or 2. Preferably m = 0.
    [0135] Groups X are preferably chosen from the following groups: alkoxy -O-R3, preferably a C1-C4 alkoxy, acyloxy -OC (O) R4 where R4 is an alkyl radical, preferably C1-C6, preferably methyl or ethyl, halogens such as Cl, Br and I or trimethylsiloxy (CHsjsSiO- and combinations of these groups. Preferably, groups X are alkoxy groups, more preferably methoxy or ethoxy groups and, better, ethoxy groups.
    [0136] The group Y, present when m is not equal to 0, is preferably a hydrocarbon group, saturated or not, more preferably a C-Cwe group, better, a C1-C4 group, for example, an alkyl group, such as such as methyl and ethyl, a vinyl group, an aryl group, for example phenyl, optionally substituted, for example, by alkyl groups such as C1-C4 alkyl. Preferably, Y represents a methyl group.
    [0137] According to a preferred embodiment of the invention, the compound of formula I 'comprises a trialkyloxysilyl group such as triethoxysilyl or trimethoxysilyl.
    [0138] Preferably, the polyoxyalkylene group of the organosilane compound (group R1) comprises less than 80 carbon atoms, more preferably less than 60.
    [0139] Examples of compounds of formula I include 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilanes of formula CH3θ- (CH2CH2θ) e-9- (CH2) 3Si (OCH3) 3 (II ') and CH3θ - (CH2CH2θ) 9-i2- (CH2) 3Si (OCH3) 3 (III '), marketed with Gelest, Inc. or ABCR, the compound of the formula CH3θ- (CH2CH2θ) 3- (CH2) 3Si (OCH3) 3 (IV '), the compounds of formula CH3O- (CH2CH2O) n- (CH2) 3Si (OC2H5) 3, where n = 21 to 24, compounds 2- [methoxy (polyethyleneoxy) propyl] trichlorosilane, 2- [acetoxy (polyethyleneoxy) propyl] trimethoxysilane of formula CH3C (O) O- (CH2CH2O) 6-9- (CH2) 3Si (OCH3) 3, 2- [acetoxy (polyethyleneoxy) propyl] triethoxy silane of formula CH3C (O) O- (CH2CH2O ) 6-9- (CH2) 3SÍ (OC2H5) 3, 2- [hydroxy (polyethyleneoxy) propyl] trimethoxysilane of the formula HO- (CH2CH2O) e-9- (CH2) 3Si (OCH3) 3, 2- [hydroxy (polyethyleneoxy) ) propyl] triethoxysilane of the formula HO- (CH2CH2O) 6-9- (CH2) 3SÍ (OC2H5) 3, compounds of formulas HO- (CH2CH2θ) δ-i2- (CH2) 3Si (OCH3) 3 and HO- (CH2CH2O) 8-i2- (CH2) 3Si (OC2H5) 3, polypropylene-bis [(3-methyldimethoxysili) propyl] oxide and compounds with two siloxane heads such as compounds (V '), (VI') or (VII1):

    [0140] Preferably, the molecular weight of the organosilane compound of the invention is in a range of 400 to 4,000 g / mol, more preferably 400 to 1,500 g / mol, better, 400 to 1,200 g / mol, and ideally 400 to 1,000 g / mol.
    [0141] When the graft is implanted in the gas phase, for example, by evaporation under vacuum, the graft can be followed, if necessary, by a step of eliminating an excess of the organosilane compound, in order to keep only the compounds of organosilane that are actually grafted onto the surface of the second inorganic coating. The non-grafted molecules are then removed. Generally, such an elimination step is implemented when the thickness of the hydrophilic coating is greater than 5 nm.
    [0142] The elimination of excess organosilane compound is implanted by rinsing and drying (liquid mode) using soapy water and / or drying.
    [0143] Preferably, the elimination is done by rinsing, followed by dry drying. A final rinse in deionized water is implanted, followed by a rinse with a cloth impregnated with an alcohol such as isopropyl alcohol.
    [0144] A temporary anti-fog layer can be obtained by depositing a film of a liquid solution containing a surfactant on the surface of the hydrophilic coating.
    [0145] The liquid solution containing a surfactant can be applied by depositing at least one droplet of said solution and then spreading it on the surface of the optical article using a cloth. The surfactant solution is generally an aqueous solution comprising 0.5 to 10%, preferably 2 to 8% by weight of the surfactant. Preferably, a surfactant is used which comprises poly (oxyalkylene) groups.
    [0146] According to a specific modality, a hydrophobic anti-fog coating can be deposited on said second inorganic layer.
    [0147] The modality that corresponds to a more hydrophobic outer layer must now be revealed in detail.
    [0148] The outermost layers also defined as anti-fog layers preferably used in this invention are those that reduce the surface energy of the article to less than 20 m J / m2. The invention is of particular interest in using top anti-fog coatings that have a surface energy of less than 14 mJ / m2 and, even better, less than 12 mJ / m2.
    [0149] The surface energy values referred to above are calculated according to the Owens Wendt method, described in the following document: Owens, D. K .; Wendt, R. G. "Estimation of the surface force energy of polymers", J. Appl. Polym. Sci. 1969, 51, 1741 to 1747.
    [0150] The top anti-fog coating according to the invention is preferably of an organic nature. By organic nature, a layer is understood to be comprised of at least 40% by weight, preferably at least 50% by weight of organic materials, in relation to the total weight of the coating layer. A preferred anti-fog topcoat is made of a liquid coating material that comprises at least one fluorinated compound.
    [0151] Hydrophobic surface coatings most often comprise silane-based compounds that have fluorinated groups, particularly perfluorocarbon or perfluoropolyether group (s). By way of example, silazane, polysilazane or silicone compounds should be mentioned that comprise one or more fluorine-containing groups such as those mentioned here above. Such compounds have been widely disclosed in the prior art, for example, in U.S. Patent Nos. 4410563, EP 0203730, EP 749021, EP 844265 and EP 933377.
    [0152] A classic method for forming an anti-fog topcoat is to deposit compounds that have fluorinated groups and Si-R, R groups representing an -OH group or a precursor thereof, such as -Cl, -NH2, -NH- or -O-alkyl, preferably an alkoxy group. Such compounds can carry out, on the surface on which they are deposited, directly or after hydrolysis, polymerization reactions and / or cross-linking with pending reactive groups.
    [0153] The preferred fluorinated compounds are silanes and silazanes that have at least one group selected from fluorinated hydrocarbons, perfluorocarbons, fluorinated polyethers such as F3C- (OC3Fe) 24-O- (CF2) 2- (CH2) 2-O-CH2 -SÍ (OCH3) 3 and perfluoropolyethers, particularly perfluoropolyethers.
    [0154] Among the fluorosilanes the compounds of the formulas can be mentioned:

    [0155] wherein n - 5, 7, 9 or 11 is a alkyl group, typically a C1-C10 alkyl group such as methyl, ethyl and propyl;
    [0156] CF3CH2CH2SÍCI3;

    [0157] where n '= 7 or 9e D as defined above.
    [0158] Compositions containing fluorosilane compounds also useful for making hydrophobic and / or oleophobic topcoats are disclosed in US 6,183,872. Such compositions comprise organic fluoropolymers containing silicon represented by the general formula below and having a numerical average molecular weight of 5 x 102 to 1 x 105.

    [0159] where RF represents a perfluoroalkyl group, Z represents a fluorine atom or a trifluoromethyl group, a, b, c, and d, each independently representing 0 or an integer equal to or greater than 1, provided that a + b + c + d + e is not less than 1 and the order of repetition units in parentheses by subscriptions a, b, c, d and d occurring in the above formula is not limited to that shown; Y represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms; X represents a hydrogen, bromine or iodine atom; R1 represents a hydroxyl group or a hydrolyzable substituent group; R1 represents a hydroxyl group or a hydrolyzable substituent group; R2 represents a hydrogen atom or a monovalent hydrocarbon group; I represents 0, 1 or 2; m represents 1, 2 or 3; and n "represents an integer equal to or greater than 1, preferably equal to or greater than 2.
    [0160] Other preferred compositions for forming the hydrophobic surface coating are those containing compounds that comprise fluorinated polyether groups, particularly perfluoropolieter groups. A particular preferred class of compositions containing fluorinated polyether groups is disclosed in US 6,277,485. The top anti-fog coatings of US 6,277,485 are at least partially cured coatings that comprise a fluorinated siloxane by applying a coating composition (typically in the form of a solution) comprising at least one fluorinated silane of the following formula:

    [0161] where RF is a monovalent or divalent polyfluoropolyether group; R2 is a divalent alkylene group, arylene group or combinations thereof, optionally containing one or more heteroatoms or functional groups and optionally substituted by halide atoms and preferably containing 2 to 16 carbon atoms; R2 is a lower alkyl group (i.e., a C1-C4 alkyl group); Y is a halide atom, a lower alkoxy group (i.e., a C1-C4 alkoxy group, preferably a methoxy or ethoxy group) or a lower acyloxy group (i.e., -OC (O) R3 where R3 is a C1-C4 alkyl group); x is 0 or 1; and y is 1 (RF is monovalent) or 2 (RF is bivalent). Suitable compounds typically have a molecular weight (numerical average) of at least about 1,000. Preferably, Y is a lower alkoxy group and RF is a perfluoropolyether group.
    [0162] The commercial compositions for making the top anti-fog coatings are the KY130 and KP 801M compositions sold with Shin-Etsu Chemical and the OPTOOL DSX composition (a fluorine-based resin comprising chemical portions of perfluoropropylene) sold with Daikin Industries .
    [0163] OPTOOL DSX is the most preferred coating material for top anti-fog coatings.
    [0164] The liquid coating material to form the anti-fog topcoat of the invention may comprise one or more of the compounds mentioned above. Preferably, such compounds or mixtures of compounds are liquid or can be made liquid by heating, thus being in a state suitable for the deposit.
    [0165] Deposit techniques for such anti-fog top coatings are very diverse, including liquid phase deposit such as dip coating, spin coating (centrifugation), spray coating or vapor phase deposit (vacuum evaporation).
    [0166] In the context of the present invention, vacuum evaporation is preferred.
    [0167] If the top anti-fog coating is applied in a liquid form, at least one solvent is added to the coating material in order to prepare a liquid coating solution with an appropriate concentration and viscosity for the coating. The deposit is followed by healing.
    [0168] The deposited top anti-fog coating preferably has a physical thickness less than 15 nm, more preferably it is in a range of 1 to 10 nm, even better than it is in a range of 1 to 5 nm. The control of the deposited thickness can be carried out by means of a quartz scale.
    [0169] The anti-fog topcoat used in this document can be used to improve resistance to the dirt mark of the finished article, which is particularly useful for optical articles. Reducing surface energy prevents the adhesion of fat deposits, such as fingerprints, tallow, sweat, cosmetics, which are thus easier to remove.
    [0170] In addition, the final optical articles preferably do not absorb light in the visible (or small) band, which means in this document that when coated on one side according to the inventive process, the optical article has a light absorption in the band visible due to coatings preferably 1% or less, more preferably less than 1% and / or a relative light transmission factor in the visible spectrum, Tv, preferably greater than 90%, more preferably greater than 95% and even more preferably greater than 96%. Preferably, both features are simultaneously satisfied and can be achieved by carefully controlling the thickness of the coatings.
    [0171] As used in this document, the Tv factor is as defined in the standard NF EN 1836 and corresponds to the wavelength range from 380 to 780 nm.
    [0172] In an alternative modality, the optical article can be colored or dyed and absorb light in the visible range.
    [0173] The final optical articles prepared according to the invention preferably have low opacity characteristics. Opacity is a measurement of transmitted light diffused more than 2.5 ° from the geometric axis of incident light. The lower the opacity value, the lower the degree of turbidity. The opacity value of the present optical articles is preferably less than 0.5% and more preferably less than 0.3%.
    [0174] The invention provides many advantages.
    [0175] The invention allows, by using a simple method, to improve the abrasion resistance properties of an optical article already coated with an abrasion resistant coating.
    [0176] Consequently, there is no need to intrinsically modify the composition of the abrasion resistant coating.
    [0177] The method of the invention allows to obtain either hydrophilic optical articles resistant to abrasion, leading to anti-fog optical articles or abrasion hydrophobic optical articles resistant to abrasion that have anti-stain properties. All of these properties are particularly useful in the eyeglass lens industry.
    [0178] Now, the present invention will be described in more detail with reference to the following examples. These examples are provided only to illustrate the present invention and should not be construed as limiting the scope and spirit of the present invention.
    [0179] The following test procedures were used to evaluate the optical articles prepared in accordance with the present invention. a) Opacity and Tv value
    [0180] The opacity value of the final optical article was measured by light transmission using the Haze-Guard Plus opacity meter from BYK-Gardner (a color difference meter) according to the ASTM D1003-00 method , which is incorporated in this document in its entirety as a reference. All references to "opacity" values in this order are by this standard. The instrument was first calibrated according to the manufacturer's instructions. Then, the sample was placed in the transmission light beam of the pre-calibrated meter and the opacity value was recorded from three different specimen locations and the average was calculated. Tv was measured using the same device.
    [0181] The "light transmittance" or "relative light transmission factor in the visible spectrum" Tv (or Çv) is also defined in the ISO 13666: 1998 standard and is measured according to the ISO 8980-3 standard (from 380 to 780 nm). b) BAYER Sand Test
    [0182] The determination of such BAYER value was conducted in accordance with Standard ASTM F 735.81. The higher the BAYER test value, the greater the abrasion resistance.
    [0183] This test consists of simultaneously stirring a glass sample and a glass specimen with an alternating motion in a tank comprising an abrasive powder (sand) with a defined particle size at a frequency of 100 cycles / minute for 2 minutes . The diffusion measurement of H "before / after" a glass sample was compared to that of a glass specimen, here an empty glass based on CR-39 (R) for which the BAYER value was fixed at 1. 0 BAYER sand value corresponds to glass specimen R = H / glass sample H. c) Bayer Abrasion Test (with Alumina) (will be referred to as ISTM Bayer):
    [0184] Bayer abrasion resistance is determined by measuring the percentage opacity of a coated and uncoated lens, before and after testing in an oscillating sand abrasive as in ASTM F 735-81, with the following modifications: the abrasive is oscillated for 300 cycles with approximately 500 g of aluminum oxide (AI2O3) ZF 152412 supplied by Specially Ceramic Grains (formerly Norton Materials) New Bond Street, PO Box 15137 Worcester, Mass. 01615-00137. Opacity is measured using a Pacific Scientific model XL-211 opacity meter. The ratio of uncoated lens opacity (end-to-end) is a measure of coating performance, with a higher ratio meaning higher abrasion resistance. d) The qualitative test known as the "n * 10 blow" test makes it possible to evaluate the adhesion properties of a film deposited on a substrate, particularly the adhesion of an anti-reflective coating to a substrate of an ophthalmic lens. Here, it is applied to assess the adhesion of the two inorganic based layers to the abrasion resistant coating.
    [0185] The same was carried out on the convex face of the lens in accordance with the procedure described in the world patent application WO 99/49097 with the use of a deformation number equal to 50.
    [0186] A tension (or cycle) consists of moving the eraser 10 times in a backward and forward motion. The operator visually checked the condition of the lenses examined at every 3 strains and up to 12 strains, then every 20, 30, 40 and 50 strains. The assessment is based on the number of stresses that the lens can withstand until a defect appears. Therefore, the higher the value obtained for the n * 10 blowing probe, the stronger the adhesion of the anti-reflective coating to the substrate. e) The thickness of the films was assessed by the ellipsometer. EXAMPLES: General Procedures: 1) Preparation of coated abrasion resistant lenses (also called hard coated lenses).
    [0187] The optical articles employed in the examples comprise an ORMA® ESSILOR substrate piano lens (6 bases) that has a diameter of 65 mm, a thickness of 1.2 mm, coated on both sides with an impact resistant primer which has a thickness of about 1 micrometer based on a W234 latex composition and deposited in it, an abrasion resistant and / or anti-scratch coating (hard coating) disclosed in example 3 of patent EP 0614957 (refractive index 1.50) , based on a hydrolyzate of GLYMO (gamma-glycidoxypropyl trimethoxysilane) and DMDES (dimethyldiethoxysilane), of colloidal silica and aluminum acetyl acetonate.
    [0188] The abrasion resistant coating was obtained by depositing and curing a composition comprising by weight, 224 parts of GLYMO, 80.5 parts of 0.1 N HCI, 120 parts of DMDES, 718 parts of colloidal silica at 30% by weight in methanol, 15 parts of aluminum acetyl acetonate and 44 parts of ethylcelosolve. The composition also comprised 0.1% of the FLUORAD ™ FC-430 (R) (3M) surfactant by weight as referred to the total weight of the composition. This abrasion resistant coating was deposited directly on the substrate. 2) Deposition of a first inorganic layer comprising SiO2.
    [0189] A Satis 1200 DLF vacuum coater equipped with a Mark II ion cannon is used for the deposition of inorganic layers.
    [0190] After positioning the lens in the vacuum chamber, the vacuum is produced at a pressure of 3.5 103 Pa (Pascal) (3.5 10 '5 mbar).
    [0191] Then, an ion cannon pretreatment using Argon ions is implanted (3A -150 V) on the lens surface for about 60 seconds and stopped.
    [0192] Then, the following component, placed in a crucible, is evaporated using an electron beam:
    [0193] Manufacturer: OPTRON
    [0194] Composition: SÍO2
    [0195] Material format: granule size between 1 and 2 mm
    [0196] and deposited in the abrasion resistant layer.
    [0197] During deposition, oxygen (O2) is introduced into the vacuum chamber so that the resulting pressure inside the chamber during the deposition step is 1.3 10'2 Pa (1.3 10'4 mbar) deposited at a rate of 0.35 nm / s. 3) Deposition of the second inorganic layer comprising SiO2.
    [0198] Then, the following component, placed in a crucible, is evaporated using an electron beam:
    [0199] Manufacturer: OPTRON
    [0200] Composition: SÍO2
    [0201] Material format: granule size between 1 and 2 mm
    [0202] During deposition, no additional gas (especially non-O2) is supplied in the vacuum coater and no ionic aid is performed.
    [0203] The pressure is 0.003 Pa (2.5 10’5 mbar). The deposit rate is 0.8 nm / s. 4) Deposition of the hydrophilic layer.
    [0204] The following material (called SIPEO) is evaporated: CH3θ- (CH2CH2θ) e-9- (CH2) 3Si (OCH3) 3
    [0205] The material is placed in a copper capsule and the capsule is placed in the middle of a tantalum evaporation crucible.
    [0206] About 12 nm of SIPEO (excess of SIPEO) are evaporated by Joule effect.
    [0207] Then, the lens is cleaned with soapy water using a sponge. It is cleaned with deionized water and then cleaned with a cloth impregnated with IPA (isopropyl alcohol). 5) Deposition of the hydrophobic layer.
    [0208] The hydrophobic material that is evaporated is Optool DSX. with Daikin.
    [0209] The DSX is placed in a copper capsule and the capsule is placed in the middle of a tantalum evaporation crucible and evaporated by Joule effect. The pressure during evaporation is 0.003 Pa (2.5 10'5 mbar).
    [0210] Several examples are made in different thicknesses for inorganic layers.
    [0211] 3 lens samples are taken for each example.
    [0212] The evaluation of the examples is reported in the following two tables. For abrasion resistance, opacity and transmittance, the value mentioned is the average of the results of the 3 samples. For the adhesion test (N10 murmurs), if all the samples do not generate a result of more than 50, the results of the 3 samples were detailed. Table 1
    Table 2

    [0213] Based on the above results and taking example 12 (Hard coated lens 1)) as a reference, it is clearly observed that depositing an inorganic silica layer on an abrasion resistant lens does not necessarily lead to an increase mechanical properties (comparative examples 5 and 6: no improvement in abrasion resistance or no adhesion). In addition, if there is no proper selection of pressure deposit conditions and thicknesses of the two inorganic layers, there is a decrease in abrasion resistance or adhesion problems (Comparative examples 7, 8 and 9).
    [0214] The examples according to invention 1 to 3 show a significant improvement in the Bayer Sand Value greater than 5.
    [0215] Finally, the deposition of a hydrophilic or hydrophobic layer in the silica bilayer of examples 4 and 13 leads to a very high improvement of Areia Bayer and ISTM Bayer.
    [0216] The deposition of a hydrophilic layer in the abrasion resistant without the silica bilayer of the examples does not lead to an ISTM Bayer greater than 5.
    权利要求:
    Claims (10)
    [0001]
    1. Method for preparing an abrasion resistant optical article characterized by the fact that it comprises: a) providing an optical article that has at least one main face that has an abrasion resistant coating; b) positioning said optical article in a vacuum deposit chamber; c) deposit a first inorganic layer comprising SiO2 on said abrasion-resistant coating and in direct contact with it by vacuum evaporation of SiO2 and / or SiOx, with 1 <x <2, in said vacuum chamber, and the thickness of said first inorganic layer is in the range of 10 to 100 nm, in which oxygen is introduced into said vacuum chamber during said evaporation; said deposit being conducted without ion assistance; d) deposit a second inorganic layer comprising SiO2 on said first inorganic layer and in direct contact with it by vacuum evaporation of SiO2 and / or SiOx, with 1 <x <2, in said vacuum chamber, the the thickness of said second inorganic layer is in a range of 70 to 300 nm, in which said deposit is conducted without ion assistance and the pressure in said vacuum chamber during the deposition of said second inorganic layer is less than the pressure during evaporation of said first inorganic layer and optionally e) apply on said second inorganic layer and in direct contact with it a hydrophilic layer or a hydrophobic antifouling layer that preferably has a thickness that is in a range of 1 to 15 nm, wherein the outermost layer of the article is said second inorganic layer or, when present, said hydrophilic or hydrophobic layer.
    [0002]
    2. Method according to claim 1, characterized by the fact that the thickness of the first inorganic layer is in a range of 10 to 30 nm and the thickness of the second inorganic layer is in a range of 70 to 150 nm.
    [0003]
    3. Method according to claim 1 or 2, characterized by the fact that it additionally comprises: e) applying a said hydrophilic or hydrophobic layer over said second inorganic layer and having a thickness that is in a range from 1 to 15 nm.
    [0004]
    Method according to any one of claims 1 to 3, characterized by the fact that the pressure inside said vacuum chamber during step c) is greater than or equal to 0.01 Pa (1 x 10'4 mbar) .
    [0005]
    5. Method according to claim 4, characterized by the fact that the pressure inside said vacuum chamber during step c) is in a range of 0.012 Pa to 0.05 Pa (1.2 x 10-4 mbar at 5 x 10-4 mbar).
    [0006]
    6. Method according to any one of claims 1 to 5, characterized in that the pressure within said vacuum chamber during step d) is in the range of 0.002 Pa to 0.005 Pa (0.2 x 10 ' 4 mbar at 0.5 x 10'4 mbar).
    [0007]
    7. Method, according to claim 1, characterized by the fact that it additionally comprises: e) applying on said second inorganic layer and in direct contact with it a hydrophilic layer that has a thickness that is in a range from 1 to 15 nm.
    [0008]
    8. Method according to claim 7, characterized in that said hydrophilic layer is applied by grafting at least one organosilane compound which has: at least one polyoxyalkylene group, which preferably comprises less than 80 carbon atoms, and - at least one Si atom that has at least one hydrolyzable group.
    [0009]
    Method according to any one of claims 1 to 8, characterized in that the deposition of the second inorganic layer is carried out without introducing an additional gas into the vacuum chamber.
    [0010]
    10. Abrasion-resistant optical article characterized by the fact that it is obtained by a method, as defined in any one of claims 1 to 8.
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    同族专利:
    公开号 | 公开日
    CA2841414C|2019-01-15|
    US20140125945A1|2014-05-08|
    AU2011370999B2|2016-01-14|
    CN103597377B|2016-08-17|
    CA2841414A1|2012-12-20|
    WO2012173596A1|2012-12-20|
    EP2718750A1|2014-04-16|
    AU2011370999A1|2014-01-16|
    CN103597377A|2014-02-19|
    EA024640B1|2016-10-31|
    US9075189B2|2015-07-07|
    WO2012173596A8|2013-08-08|
    EA201301276A1|2014-03-31|
    BR112013032071A2|2016-12-13|
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    法律状态:
    2018-07-31| B25A| Requested transfer of rights approved|Owner name: ESSILOR INTERNATIONAL (FR) |
    2018-12-26| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-06-09| B09A| Decision: intention to grant|
    2020-11-10| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/06/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/US2011/040201|WO2012173596A1|2011-06-13|2011-06-13|Method for obtaining optical articles having superior abrasion resistant properties, and coated articles prepared according to such method|
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