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    • 专利摘要:
    transparent optical article having a reduced yellowing appearance. the present invention relates to a transparent optical article (for example, an ophthalmic lens) comprising a thermo-plastic substrate and a dye that inhibits, at least partially, light having a wavelength ranging from 400 to 460 nm and an optical brightener to counterbalance, at least partially, the color given to the transparent optical article by the dye, in which the said optical brightener emits fluorescence light at a wavelength ranging from 400 to 460 nm and is incorporated in a fused layer or bonded to the thermoplastic substrate. said optical brightener allows the perception of said optical article as less yellow, and even colorless, to a user or an observer. in addition, uv absorbers that may be present on the thermoplastic substrate do not interact negatively with the optical brightener.
    公开号:BR112016013082B1
    申请号:R112016013082-0
    申请日:2013-12-23
    公开日:2021-02-23
    发明作者:Aref Jallouli；Haifeng Shan；Gilles Baillet
    申请人:Essilor International；
    IPC主号:
    专利说明:

    BACKGROUND OF THE INVENTION 1. Field of the invention
    [001] The present invention relates to the field of optics, more in particular to transparent optical articles and preferably an ophthalmic lens, which maintains an essentially colorless appearance, at the same time that it comprises an optical filter designed to protect from blue light and, optionally, from UV light. 2. Description of the related technique
    [002] The visible light as captured by humans extends approximately over a spectrum ranging from a wavelength of 380 nm to a wavelength of 780 nm. The part of this spectrum, which ranges from about 380 nm to about 500 nm, corresponds to a high energy, essentially blue light.
    [003] Many studies (see, for example, Kitchel E., "The effects of blue light on ocular health", Journal of Visual Impairment and Blindness Vol. 94, No. 6, 2000 or Glazer-Hockstein et al., Retina, Vol. 26, No. 1, page 1-4, 2006) suggest that blue light (about 430 nm) has phototoxic effects on the health of the human eye, and especially on the retina.
    [004] In reality, studies of ocular photobiology (Algvere PV et al., "Age-Related Maculopathy and the Impact of the Blue Light Hazard», Acta Ophthalmo. Scand., Vol. 84, p. 4-15, 2006) and clinical trials (Tomany SC et al., "Sunlight and the 10-Year Incidence of Age-Related Maculopathy. The Beaver Dam Eye Study», Arch Ophthalmol. Vol. 122. pages 750-757, 2004) demonstrated that an exposure excessively prolonged or intense blue light can induce serious ophthalmic diseases such as age-related macular degeneration (ARMD) or cataracts.
    [005] Therefore, it is recommended to limit exposure to potentially harmful blue light, in particular for the wavelength band with an increased hazard (see especially Table B1, ISO 8980-3: 2003 (E) regarding function hazardousness of blue light B (À)).
    [006] For this purpose, it may be advisable for a spectacle wearer to use an ophthalmic lens in front of each of both eyes that prevents or limits the transmission of phototoxic blue light to the retina. These lenses can also provide greater visual performance due to a greater sensitivity to contrast.
    [007] It has already been suggested, for example in patent application WO 2008/024414, to cut at least partially the worrying part of the blue light spectrum from 400 nm to 460 nm by means of lenses comprising a film that partially inhibits light in the range of adequate wavelengths, through absorption or through reflection. This can also be done by incorporating a yellow dye into the optical element.
    [008] However, blocking blue light affects color balance, color vision if you look through the optical device and the color in which the optical device is perceived. In reality, optical devices that block blue light by incorporating a dye that inhibits, at least partially, light with a wavelength ranging from 400 to 460 nm appear yellow, brown or amber. This is technically unacceptable for many ophthalmic applications, and can interfere with normal color perception by the user, if the device is an ophthalmic lens.
    [009] Efforts have been made to compensate for the softening effect of conventional blue blocking filters. For example, blue blocking lenses have been treated with additional dyes, such as blue, red or green dyes, to compensate for the yellowing effect. However, this technique undesirably reduces the overall transmission of wavelengths of light different from the wavelengths of blue light, which results in attenuation of light for a lens wearer.
    [0010] In view of the background, there is a need for an optical article capable of blocking, at least partially, blue light that can still provide aesthetic aspects of acceptable color, that is, that is perceived as practically colorless by someone who observes the article optical. An acceptable global level of light transmission is also required, as well as an acceptable color perception for a user, that is, the optical article must not dramatically impair color vision by the user in the case of an ophthalmic system. In particular, there is a need for an optical article that allows selective blocking of wavelengths of blue light, while transmitting at least 80% of visible light at the same time.
    [0011] The present inventors have found that optical brighteners, also called fluorescent bleaching agents (FWA), optical bleaching agents (OBA) or fluorescent brightening agents (FBA), could be used as a means to counterbalance color , that is, to minimize, and preferably eliminate, the change in color perception that results from the blue blocking by a blue light blocking dye incorporated in an optical system, since the blue light emitted by the optical brightener can compensate for the decrease blue color of the material treated by the dye and restore the original colorless appearance.
    [0012] The present inventors also found that UV absorbers, which are often incorporated into substrates of optical articles to reduce or prevent UV light from reaching the retina (particularly in ophthalmic lens materials), could interfere with the ability of optical brighteners to emit fluorescence light. Therefore, careful control of the respective locations of the blue light blocking dye, UV absorber and optical brightener is necessary to allow said optical brightener to effectively balance the color imparted by the dye, while not impairing the UV blocking function. original of the optical article. SUMMARY OF THE INVENTION
    [0013] In order to solve the needs of the present invention and to remedy the mentioned disadvantages of the prior art, the applicant provides a transparent optical article comprising a thermoplastic substrate and:
    [0014] - at least one dye A that inhibits, at least partially, light having a wavelength ranging from 400 to 460 nm, preferably from 420 to 450 nm, and
    [0015] - at least one optical brightener B to counterbalance, at least partially, the color given to the transparent optical article by dye A, in which said at least one optical brightener B emits fluorescence light at a wavelength that it ranges from 400 to 460 nm, preferably from 420 to 450 nm, and is incorporated in at least one layer L1 fused or bonded to the thermoplastic substrate, and in which said dye A and said optical brightener B are different from each other.
    [0016] The combined use of an optical brightener B in layer L1 and a dye A (also referred to as blue light blocking dye or yellow dye in this specification) on the substrate and / or at least one layer coated on the substrate of the transparent optical article simultaneously protects the user from blue light and effectively mask the yellow color conferred by the dye.
    [0017] Furthermore, when the substrate of the optical article comprises UV absorbers, UV protection is also maintained and the operation of the optical brightener is not affected by said UV absorbers. BRIEF DESCRIPTION OF THE DRAWINGS
    [0018] The previous objectives, characteristics and advantages, and others, of the present invention will become immediately evident to those skilled in the art from a reading of the detailed description that follows, when considered together with the attached drawings, in whereas figures 1-4 represent the light transmission curves between 350 and 750 nm of the various lenses and comparative lenses described in the experimental part (respectively, the lenses of comparative examples 1, 2 and 3 and the lens of example 1) . DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
    [0019] As used herein, when an article comprises one or more layer (s) or coating (s) on its surface, "deposition of a layer or coating on the article" means that a layer or coating is deposited on the uncovered (exposed) surface of the outer coating of the article, that is, the coating that is furthest from the substrate.
    [0020] As used herein, a coating / layer that is "on" a substrate / coating or that has been deposited "on" a substrate / coating is defined as a coating / layer that (i) is positioned above the substrate / coating, (ii) is not necessarily in contact with the substrate / coating, that is, one or more intermediate coating (s) may be interspersed between the substrate / coating and the relevant coating / layer (however, it is preferably in contact with said substrate / coating), and (iii) does not necessarily completely cover the substrate / coating. When "a coating / layer 1 is referred to as being located under a coating / layer 2", it should be understood that the coating / layer 2 is further away from the substrate than the coating / layer 1.
    [0021] In the present description, an optical article is understood to be transparent when the observation of an image through said optical article is captured without significant loss of contrast, that is, when an image is obtained through said optical article without adversely affecting the image quality. This definition of the term "transparent" can be applied to all objects qualified as such in the description.
    [0022] The transparent optical article according to the invention is preferably an optical lens or blank lens, more preferably an ophthalmic lens or blank lens.
    [0023] The term "ophthalmic lens" is used to mean a lens adapted to an eyeglass frame to protect the eye and / or correct vision. Said lens can be chosen from afocal, single, bifocal, trifocal and progressive lenses. Although ophthalmic optics is a preferred field of the invention, it will be understood that this invention can be applied to transparent optical elements of other types, such as, for example, lenses for optical instruments, filters particularly for photography or astronomy, lenses for optical sights, eye visors, optics for lighting systems, etc.
    [0024] The transparent optical article comprises a thermoplastic substrate and at least one coated layer on the substrate. If it is an optical lens, it can be coated on its main convex side (front), main concave side (back), or on both sides. The transparent optical article can also be a flat article.
    [0025] A substrate, in the sense of the present invention, is to be understood as meaning an uncoated substrate, and generally has two main faces. The substrate may in particular be an optically transparent material having the shape of an optical article, for example an ophthalmic lens intended to be mounted on glasses. In this context, the term "substrate" is understood to mean the constituent material of the transparent base of the optical lens and, more particularly, of the ophthalmic lens. This material acts as a support for the stack of one or more coatings or layers.
    [0026] The substrate of the article of the invention is an organic glass made of a thermoplastic material, generally chosen from transparent materials of ophthalmic quality used in the ophthalmic industry.
    [0027] To be mentioned as especially preferred classes of polymeric materials for substrates are polycarbonates such as those derived from bisphenol-A, polyamides, polyesters, polyurethanes, polysulfones, amorphous polyolefins, polyethylene, polypropylene, poly (acrylonitrile), poly (vinyl acetate), poly (vinyl chloride), poly (butadiene), cyclic olefin copolymers, polystyrene, poly (met) acrylic resins such as poly (met) methyl acrylate, poly (n methacrylate) -butyl), poly (isobutyl methacrylate), poly (ethyl methacrylate), polycarbonate / polyester mixtures, poly (vinyl alcohol), polyvinylformal, cellulose butyrate acetate, polyvinyl acetate, (ethylene / vinyl acetate) copolymers saponified, copolymers of any of these, and mixtures of any of these.
    [0028] The preparation of thermoplastic substrates, for example, by injecting a molten thermoplastic resin into a substrate-forming cavity kept closed under a clamping force, is well known to those skilled in the art and is described, for example, in US 2009 / 283926, US 2009/283924 and US 6,328,446.
    [0029] Preferably, the thermoplastic substrate of the optical article contains less than 1% by weight of optical brighteners relative to the weight of said substrate, ideally it does not contain any optical brightener.
    [0030] Said thermoplastic substrate generally contains at least one UV absorber, preferably having the ability to block, at least partially, light having a wavelength shorter than 400 nm, preferably UV wavelengths below 385 or 390 nm. The best UV absorbers do not absorb any substantial amount of visible light.
    [0031] Said UV absorbers protect both the user's eye from UV light and the substrate material itself, thus preventing the attack by atmospheric agents and becoming brittle and / or yellow.
    [0032] Polycarbonates are the preferred substrate materials, in particular polycarbonates containing UV absorbers. Polycarbonates that do not have UV absorbers will block only wavelengths of light below 290 nm.
    [0033] Suitable UV absorbers include, without limitation, substituted benzophenones such as 2-hydroxybenzophenone, substituted 2-hydroxybenzophenones disclosed in U.S. Pat. No. 4,304,895, 2- (2-hydroxyphenyl) -benzotriazoles, the 2-hydroxy-5-acryloxyphenyl-2H-benzotriazoles disclosed in U.S. Pat. No. 4,528,311.2- (3'-metallyl-2'-hydroxy-5'-methyl-phenyl) benzotriazole, and allylhydroxymethylphenyl-benzotriazole.
    [0034] Methods for incorporating UV absorbers into the substrate of the optical article are well known. This is preferably accomplished by mixing the UV absorbers in the composition of the thermoplastic substrate.
    [0035] According to the invention, the dye A and the optical brightener B are incorporated in the transparent optical article. Dye A is preferably incorporated into the substrate and / or in at least one coated layer on the substrate. Optical brightener B is preferably incorporated into at least one L1 layer fused to the thermoplastic substrate, or directly or indirectly bonded, in general, in an adhesive manner to the thermoplastic substrate. In the context of the present invention, "directly" means that there is a direct contact between the materials and a layer that is melted with a substrate continues to be considered to be coated on the substrate.
    [0036] In the systems according to the invention, dye A and optical brightener B can be incorporated together in the same L1 layer or separately in different locations, for example in (at least) two different layers L1 and L2, or can be A combination of these modalities is implemented, while continuing to obtain the advantages and benefits of the invention in terms of health and aesthetic appearance.
    [0037] In reality, dye A can be incorporated, without limitation, in the thermoplastic substrate and / or in said at least one L1 layer and / or in at least one L2 layer coated on the thermoplastic substrate which is different from the L1 layer, while optical brightener B is necessarily incorporated at least in the L1 layer. When dye A is not incorporated in the substrate or in the L1 layer, it is necessarily incorporated in an L2 layer.
    [0038] If the dye and optical brightener are included in (at least) two different layers, these layers are not necessarily deposited on the same side of the transparent optical article. They can be deposited on either side of the transparent optical article (which can be convex, concave or flat), or on both sides of the transparent optical article. Although layers L1 and L2 (when present) are not necessarily deposited on the same face of the optical article, in a preferred embodiment, the transparent optical article comprises at least one L2 layer (containing at least one dye A) which is coated on the same - the main surface of the substrate than the L1 layer. In this case, the L2 layer is preferably located under the L1 layer in the stacking order, that is, it is interspersed between the thermoplastic substrate and the L1 layer and is preferably in direct contact with the substrate and the L1 layer. However, the L2 layer may also be deposited on the L1 layer.
    [0039] When the optical article has anterior and posterior main surfaces, the L1 layer is preferably formed on the anterior (convex) main surface of the optical article, which is preferably a lens. The same applies to the L2 layer, when present. When the optical article has anterior and posterior main surfaces, its posterior surface is preferably not coated with any layer containing optical brighteners, such as an L1 layer. In the preferred embodiment of the invention, dye A is incorporated into the thermoplastic substrate and optical brightener B is incorporated into at least one L1 layer formed on the front main surface of the optical article.
    [0040] When the L2 layer (containing at least one dye A) is present, it is preferably fused or directly bonded (generally in an adhesive way) to the substrate. In this case, the L1 layer is considered to be indirectly bonded or fused to the thermoplastic substrate. Said layer L1 is preferably fused or bonded (generally in an adherent manner) to layer L2.
    [0041] In other embodiments, the L2 layer may constitute or form part of, without limitation, a primary coating, a hard coating or an anti-reflective coating, which will be described later. In this case, the L2 layer is preferably a coating layer or layer deposited on the L1 layer, or on a main surface of the substrate that does not comprise any L1 layer.
    [0042] When the L2 layer is not present, the L1 layer is preferably fused or directly linked to (that is, in direct contact with) the substrate.
    [0043] The L1 layer preferably has a thickness less than or equal to 2 mm, more preferably less than or equal to 1 mm, better still ranging from 100 to 500 μm. When present, the L2 layer preferably has a thickness less than or equal to 2 mm, more preferably less than or equal to 1 mm, even better ranging from 100 to 500 μm.
    [0044] Preferably, the L1 layer contains less than 1% by weight of UV absorbers relative to the weight of said layer, ideally it does not contain any UV absorber. Preferably, the L2 layer contains less than 1% by weight of UV absorbers relative to the weight of said layer, ideally it does not contain any UV absorber. It is crucial that the L1 layer or the other layers that incorporate the optical brightener contain little or no UV absorber, so that the optical brightener is able to effectively counterbalance the color imparted by the dye without suffering from "interference" caused by the presence of a UV absorber in its close environment. On the contrary, an L2 layer incorporating the blue light blocking dye may comprise UV absorbers.
    [0045] Various dyes and / or several optical brighteners can be incorporated into the substrate and / or the same or different layers deposited on the substrate surface.
    [0046] In some applications, it is preferred that the main surface of the substrate, coated with the L1 layer and, when present, the L2 layer, is further coated with one or more functional coating (s) to improve the optical and / or mechanical properties. The term "coating" is intended to mean any layer, stack of layers or film that may be in contact with the substrate and / or with another coating, for example a sol-gel coating or a coating made of an organic resin. A coating can be deposited or formed using various methods on the L1 layer or, when present, the L2 layer, including wet processing, gaseous processing and film transfer. These functional coatings used classically in optics can be, without limitation, an impact resistant and / or adhesion primer, an abrasion resistant and / or scratch resistant coating, an anti-reflective coating, a polarized coating, a photochromic coating, or an antistatic coating, or a stack made of two or more of these coatings, especially an impact resistant primary coating coated with an abrasion and / or scratch resistant coating.
    [0047] Coatings resistant to abrasion and / or scratches (hard coatings) are preferably hard coatings based on poly (meth) acrylates or silanes. The hard coatings resistant to abrasion and / or scratches recommended in the present invention include coatings obtained from compositions based on silane hydrolysates (sol-gel process), in particular compositions based on epoxysilane hydrolysates, such as those described in US patent application, US 2003/0165698 and US 4,211,823.
    [0048] The primary coatings that improve the impact resistance and / or the adhesion of the additional layers in the final product are preferably polyurethane latexes or acrylic latexes. Primary coatings and abrasion resistant and / or scratch resistant coatings can be selected from those described in application WO 2007/088312. The primary coating generally promotes the adhesion of the hard coating to the substrate.
    [0049] The anti-reflective coating, which improves the anti-reflective properties of the final optical article by reducing the reflection of light at the article-air interface over a relatively wide range of the visible spectrum, can be any anti-reflective coating classically used in the field of optics, in particular in ophthalmic optics. As is well known, antireflective coatings traditionally comprise a monolayer or a multilayer cell consisting of dielectric or sol-gel materials. These are preferably multilayer coatings, comprising layers with a high refractive index (HI, n> 1.5) and layers with a low refractive index (LI, n <1.5).
    [0050] The structure and preparation of the anti-reflective coatings are described in more detail in the patent application WO 2010/109154 and WO 2012/153072.
    [0051] Coatings such as primers, hard coatings and anti-reflective coatings according to the invention can be deposited using methods known in the art, including rotational coating, dip coating, spray coating, evaporation, sputtering, chemical vapor deposition and lamination.
    [0052] The three preferred embodiments of the invention and the methods of manufacturing the corresponding optical articles will now be described in detail.
    [0053] In a first preferred embodiment of the invention, the transparent optical article comprises a thermoplastic substrate in which the blue light blocking dye A is incorporated, while the optical brightener B is incorporated in the L1 layer.
    [0054] In a second preferred embodiment of the invention, the transparent optical article comprises a thermoplastic substrate, at least one L2 layer and at least one L1 layer coated on the substrate in that order, in which dye A is incorporated into said at least one layer L2 and the optical brightener B is incorporated in said at least one layer L1.
    [0055] In a third preferred embodiment of the invention, the transparent optical article comprises a thermoplastic substrate and at least one layer L1 coated on the substrate, in which both dye A and optical brightener B are incorporated in said at least one layer L1 .
    [0056] In these three modalities, the layers L1 and L2 are preferably applied on the substrate of the optical article as preformed molded laminates, as described below.
    [0057] The dye can be incorporated into the substrate by methods well known in the art, for example:
    [0058] I. methods of impregnation or imbibition consisting of immersing the substrate in a hot-colored bath based on organic solvent and / or water, preferably an aqueous-based solution, for several minutes. Substrates, such as organic lens substrates, are very often colored in the material structure by immersion in aqueous color baths, heated to temperatures of the order of 90 ° C, and in which the dye has been dispersed. Thus, the dye diffuses under the substrate surface and the color density is obtained by adjusting the amount of dye that diffuses in the substrate body,
    [0059] II. the diffusion methods described in JP 2000-314088 and JP 2000-241601, involving a temporary impregnable coating,
    [0060] III. non-contact staining using a sublimable material, as described in US 6534443 and US 6554873, or
    [0061] IV. incorporation of a blue absorption dye during the manufacture of the substrate itself, for example by molding or injection molding, if the dye is sufficiently resistant to the high temperatures present during molding or injection molding.
    [0062] Several methods familiar to those skilled in the optical manufacturing technique are known to incorporate the dye (and / or the optical brightener) in an L1 and / or L2 layer (or in a pre-formed film, here called "laminate" ). The blue light blocking dye can be deposited at the same time as the layer, that is, when the layer is prepared from a liquid coating composition, the dye can be incorporated (directly or, for example, as particles dye-impregnated) or dissolved in said coating composition before being applied (mixing in situ) and hardened on the substrate surface.
    [0063] The dye (and / or the optical brightener) can also be included in a coating in a separate process or sub-process. For example, the dye can be included in the coating after its deposition on the surface of the substrate, using a dipping method similar to that mentioned for the coloring of the substrate, that is, by means of a dye bath at elevated temperatures, through of the diffusion method disclosed in US 2003/0020869, in the applicant's name, through the method disclosed in US 2008/127432, in the applicant's name, which uses a printing primer that is printed using an inkjet printer, through the method disclosed in US 2013/244045, in the applicant's name, which involves printing with a sublimation dye by means of a thermal transfer printer, or through the method disclosed in US 2009/047424, in the applicant's name, which uses a porous layer to transfer a coloring agent to the substrate. The dye can also be sprayed onto a surface before the coating is cured (for example, thermally or UV cured), dried or applied.
    [0064] When inkjet printing is implemented, it is generally necessary to modify the surface of the article to receive the ink, typically applying a receptive coating of ink on the surface of the article. The ink receptive coating can be a coating that can be dyed permanently or a coating that can be dyed temporarily, being used as a temporary support from which the dyes are transferred to the article. The dyes can be transferred on the substrate itself or on a substrate coating, adjacent to the receptive ink coating. Inkjet printing for dyeing a substrate or coating is described in more detail in US 2013/0230649, in the applicant's name.
    [0065] The methods for incorporating an optical brightener B into a substrate or coating are generally the same as those disclosed for the incorporation of dyes. Obviously, combinations of several of the methods described herein can be used to obtain a transparent optical article having a dye A and an optical brightener B incorporated therein.
    [0066] The L1 and / or L2 layers containing the dye A and / or the optical brightener B can also be prepared as films or thin laminates that will subsequently be transferred, laminated, melted or glued to the substrate. This is the preferred method for obtaining a substrate coated with layers L1 and / or L2.
    [0067] When layer L1 (or layer L2) is melted with the substrate of the optical article, the substrate and layer L1 (or layer L2) are preferably formed from the same polymeric material (preferably polycarbonate), to obtain more permanent contact between the substrate and the layer is easily achieved. Both materials must be at least compatible with each other. However, when layer L1 or L2 is adhesive-bonded to the substrate, there is no requirement to use the same material in the layer and the substrate.
    [0068] A preferred method for applying the L1 or L2 layer to the substrate is the post-injection pressure laminating process, which is a method of laminating a film over an injection-molded thermoplastic substrate that resides in a molding machine by injection. It involves the formation of a film or laminate that contains the dye and / or the optical brightener in a first stage, preferably by molding a laminate such as a laminate to polycarbonate, and then gluing said laminate to the substrate using the method disclosed in US 2009/283926. This technique involves the deposition of a complete measured unpressurized load of curable glue or adhesive on the center of a substrate, immediately after the preparation of said substrate by injection molding, while the substrate still resides in the injection molding machine. Then, the laminate is inserted between the glue and a machine insert, the mold is closed and a clamping force is applied to finely spread the glue between the laminate and the substrate. The glue, which is preferably an acrylate-based glue, can be cured using the heat transferred from the mold and the decreasing residual heat of the substrate, and provides an adhesive layer that bonds the laminate to the substrate. The glue could also be deposited on the surface of the laminate to be glued to the substrate. With an appropriate choice of glue or adhesive, a tightly bonded L1 or L2 layer / substrate interface can be obtained, even if the layer material is different from the substrate resin. In this method, the dye or optical brightener can also be mixed in the curable glue (thus forming, after curing, an L1 or L2 layer of cured glue), and the laminate applied can be a functional film.
    [0069] US 2009/283924, in the applicant's name, discloses a variant of this technique using a thermoplastic adhesive instead of a curable glue, said hot melting product being applied as a uniformly thin layer on the film / laminate before load the film / laminate into the injection molding machine. The decreasing residual heat of the substrate present in the injection molding machine and the applied pressure causes the film / laminate to be intimately connected to the substrate. In this method, the dye or optical brightener can also be mixed in the thermoplastic adhesive, and the applied laminate can be a functional film.
    [0070] Another method for applying the L1 or L2 layer to the substrate is an overmoulding method called film insertion molding (FIM), which injects the fused thermoplastic resin against the surface of a preformed film or laminate (preferably formed) by molding) to create a fused bond between the lens and the film / laminate. The method of molding said resin onto the film / laminate involves placing the film / laminate containing the dye and / or the optical brightener in the empty cavity of the injection molding machine. The molten thermoplastic resin is then injected into the mold cavity and against the film / laminate and injection molded so that the high temperature fuses the juxtaposed film / laminate layer, causing it to fuse with the substrate of the later solidified optical article. This technique is described, for example, in Pat. No. 5,827,614, Pat. No. 6,328,446, Pat. No. 6,814,896 and Pat. No. 6,659,608 and requires that the film / laminate material applied and the substrate material be the same or compatible with each other, to obtain an effective fusion of the materials.
    [0071] The amount of optical brightener used in the present invention is an amount sufficient to provide a transparent optical article that does not have a yellow appearance, while the amount of dye used in the present invention is an amount sufficient to provide satisfactory protection from blue light. .
    [0072] The amount of optical brightener incorporated in a layer coated on (or melted with) the substrate is preferably less than 200 ppm relative to the weight of said layer, more preferably less than 50 ppm.
    [0073] When incorporated into the substrate, the blue light blocking dye is used in an amount less than 50 ppm relative to the weight of said substrate, preferably less than or equal to 5 ppm.
    [0074] When incorporated in a coated layer on the substrate (such as an L1 or L2 layer), the blue light blocking dye is used in an amount less than 5000 ppm relative to the weight of said layer, preferably less than 500 ppm .
    [0075] Naturally, the respective amounts of optical brightener and blue light blocking dye have to be adapted to produce a colorless, transparent element. In particular, those skilled in the art should understand that the desired amount of optical brightener will vary depending on several factors including the nature and amount of the dye that is used. To that end, the optimal amounts of each compound can be determined by simple laboratory experiments.
    [0076] Obviously, the transparent optical article according to the invention can only appear colorless if none of its substrates and coatings are dyed.
    [0077] As used here, a dye can refer to either a pigment or a dye, that is, it can be soluble or insoluble in your vehicle. It can be used alone or in combination.
    [0078] The chemical nature of dye A is not particularly limited, provided that it has an absorption peak, ideally a maximum absorption peak, within the range of 400-460 nm, preferably in the range of 420-450 nm. Preferably, dye A which acts as a means to inhibit, at least partially, light having a wavelength ranging from 400 to 460 nm, selectively inhibits light within the range of 400 nm - 460 nm, and more preferably within from the range of 420 nm - 450 nm. As used herein, a medium "selectively inhibits" a range of wavelengths if it inhibits at least some transmission within the range, while having little or no effect on the transmission of visible wavelengths outside the wavelength range.
    [0079] The one or more dyes incorporated in the transparent optical article preferentially absorb radiation in such a way that they inhibit from 1 to 50% of the light having a wavelength ranging from 400 to 460 nm, more preferably from 10 to 40%, ideally from 10 to 30%. They preferentially inhibit from 1 to 50% of the light having a wavelength ranging from 420 to 450 nm, more preferably from 10 to 40%, ideally from 10 to 30%. These absorptions can be controlled by the concentration of the dye and are measured against the amount of light that would be transmitted at the same wavelengths in the absence of the dyes.
    [0080] The blue light blocking dye can be chosen, without being restricted to these families, from the families of perylene, coumarin, porphyrin, acridine, indolenine (which is a synonym for 3H-indole) and indole-2- ilidene.
    The preferred blue light blocking dyes have a narrow absorption band in the 400-460 nm range of the electromagnetic spectrum, preferably at 420-450 nm. Ideally, said absorption band is centered around 430 nm.
    [0082] The most preferred dye according to the invention is perylene, which exhibits ideal spectral characteristics and interesting injection processability properties. In reality, perylene is a selective yellow dye, which does not absorb, or absorbs very little, in the regions of the visible spectrum outside the wavelength range of 400-460 nm.
    [0083] As is well known, optical brighteners are substances that absorb light in the UV and violet region (usually at 340370 nm) and emit light by fluorescence mainly in the blue region of the visible spectrum. They can be used alone or in combination.
    [0084] The chemical nature of the optical brightener is not particularly limited, provided that it is capable of emitting fluorescence light, ideally maximum fluorescence, at a wavelength ranging from 400 to 460 nm, preferably from 420 to 450 nm .
    [0085] Preferably, the optical brightener absorbs less than 30% of the light having a wavelength ranging from 400 to 460 nm, more preferably less than 20%, even more preferably less than 10%, ideally less than 5%. Preferably it absorbs less than 30% of the light having a wavelength ranging from 420 to 450 nm, more preferably less than 20%, even more preferably less than 10%, ideally less than 5%. Said optical brightener preferably does not have a peak of maximum absorption, better still no peak of absorption, within the range of 400-460 nm, preferably in the range of 420-450 nm.
    [0086] The optical brightener can be chosen, without being restricted to these families, from stilbenes, carboestirilas, coumarinas, 1,3-diphenyl-2-pyrazolines, naphthalimides, combined heteroaromatics (such as pyrenyl triazines or other combinations of heterocyclic compounds such as thiazoles, pyrazoles, oxadiazoles, fused polyaromatic systems or triazines, directly connected to each other or via a conjugated ring system) benzoxazoles, in particular benzoxazoles substituted in position 2 with a conjugated ring system, preferably comprising ethylene groups, phenylethylene, stilbene, benzoxazole and / or thiophene. Preferred families of optical brighteners are bis-benzoxazoles, phenylcoumarins, methylcoumarins and bis- (styryl) biphenyls, which are described in more detail in AG Oertli, Plastics Additives Handbook, 6th Edition, H. Zweifel, D. Maier, M Schiller Editors, 2009.
    [0087] Specific examples of commercially available bis-benzoxazole optical brighteners are Eastman Chemical's Eastobrite® compounds, such as Eastobrite® OB, Eastobrite® OB-1 and Eastobrite® OB-3, Clariant's Hostalux® compounds, such as Hosta - lux ACK, Hostalux CP01, Hostalux EBU, Hostalux EF, Hostalux ERE, Hostalux EREN, Hostalux ES2R, Hostalux ESR, Hostalux ETB 300, Hostalux ETBN, Hostalux KCB, Hostalux KS, Hostalux KS1B, Hostalux KSB3, Hostalux KSC, Hostalux KSN, Hostalux NR, Hostalux NSM, Hostalux PFC, Hostalux PFCB, Hostalux PN, Hostalux PNB and Hostalux PR, Whiteitluu® compounds (styryl-bis-benzoxazoles) from Sumitomo Chemical Co., such as Whitefluor® B, Whitefluor® PEN, Whitefluor® PHR , Whitefluor® HCS, Whitefluor® PCS.
    [0088] Specific examples of commercially available methyl coumarin optical brighteners are Eccowhite® compounds from Eastern Color & Chemical Co., such as Eccowhite 1132 MOD, Eccowhite 2013, Eccowhite 2790, Eccowhite 5261, Eccowhite AEA-HF, Eccowhite Nylon FW , Eccowhite OP, Eccowhite PSO, Eccowhite DM-04 MOD.
    [0089] Another useful category of optical brighteners is BASF's Tinopal® family, which comprises bis-benzoxazole and bis- (styryl) biphenyl compounds, such as Tinopal ABP-A, Tinopal ABP-X, Tinopal ASP, Tinopal BPO, TinopalEC, Tinopal HST, Tinopal HW, Tinopal MSP, Tinopal NP, Tinopal SPP-N, Tinopal SPP-Z, Tinopal UP HC DD, Tinopal UP HC, Tinopal CBS-X and Tinopal® OB.
    [0090] Other useful optical brighteners that can be used in the present invention are described in Fluorescent Whitening agents, Anders G. EQS, Environmental quality and safety (Suppl. Vol IV) Georg Thieme Stuttgart 1975.
    [0091] Preferred optical brighteners have a high fluorescence efficiency, that is, they re-emit as visible light an important proportion of the energy they absorbed.
    [0092] The most preferred optical brighteners are: • 2,2 '- (1,2-ethylenediildi-4,1-phenylene) bisbenzoxazole, marketed by Eastman Chemical under the trade name Eastobrite® OB-1, having the following structure:
    • 2,5-thiophenenediylbis (5-tert-butyl-1,3-benzoxazole), marketed by BASF under the trade name Tinopal® OB, having the following structure:

    [0093] According to the invention, a particular yellow dye is associated with an optical brightener having a fluorescence emission that will better correspond to the absorption spectrum of said dye, and vice versa. The nature of the dye and optical brightener allows adjustment of the positions of the absorption / emission peaks.
    [0094] In a preferred embodiment, the transparent optical article according to the invention includes a dye A and an optical brightener B such that the difference (expressed in absolute value) between the maximum absorption value Àmax (A) of the dye A and the maximum fluorescence emission value Àmax (B) from optical brightener B is less than 15 nm, more preferably less than 10 nm and ideally less than 5 nm. In the context of the present application, Àmax (A) and Àmax (B) are measured in dichloromethane.
    [0095] The combination of perylene as a blue light blocking dye and 2,5-thiophenenediylbis (5-tert-butyl-1,3-benzoxazole) (Tinopal® OB) as an optical brightener is particularly preferred, because the properties The fluorescence values of the latter correspond perfectly to the absorption spectrum of perylene. The wavelength of the maximum fluorescence emission of Tinopal® OB is 432 nm, while perylene has a maximum absorption at 434 nm.
    [0096] The transparent optical article according to the invention has improved color properties that can be quantified by the whiteness index Wi and the yellowing index Yi.
    [0097] The assessment of the whiteness effect of optical brightener B, in other words, the degree of whiteness of the inventive transparent optical article, can be carried out by means of colorimetric measurements, based on the CIE X, Y, Z tristimulus values, as described in the ASTM E313-73 (1993) and ASTM D 1925-70 (1988) standards. The transparent optical article according to the invention preferably has a high whiteness index Wi, i.e., greater than 40, as measured according to ASTM E-313-73. Wi is calculated using the Taube equation (Wi = 4B-3G, with parameters B (blue) and G (green) determined from the tri-stimulus values X, Y, Z with G = Y and B = 0.847 Z).
    [0098] The transparent optical article according to the invention preferably has a low yellowing index Yi, that is, less than 10, more preferably less than 5, as measured according to ASTM D-1925. Yi can be determined from the CIE tristimulus values X, Y, Z through the relationship: Yi = 128 X - 106 Z / Y.
    [0099] The transparent optical article according to the invention preferably has a relative light transmission factor in the visible spectrum Tv greater than 80%, more preferably greater than 85%. The Tv factor is as defined in the NF EN 1836 standard and corresponds to the wavelength range of 380-780 nm.
    [00100] Now, the present invention will be described in more detail with respect to the following examples, which are provided for illustrative purposes only. EXAMPLES I. Preparation of the lenses
    [00101] Perylene was used as dye A, while Tinopal® OB was used as optical brightener B. The lenses were prepared using the overmolding method disclosed in US 6,328,446, using two different polycarbonate materials, compatible with each other. First, a 900 μm thick polycarbonate laminate (Makrolon 3158, from Bayer, containing no UV absorber) was placed in the empty mold cavity of an Arburg 320 injection molding machine, in order to expose the concave surface of said laminate. The laminate (76 mm in diameter, 0.9 mm in Central Thickness, with base 6 curvature) was previously molded from a flat lens. Then, Panijl 1250ZT resin from Teijin was injected into the mold cavity against the concave surface of the laminate. Said resin is a standard ophthalmic polycarbonate that includes a UV absorber. Injection molding was then carried out according to conditions well known to the person skilled in the art.
    [00102] Lenses (76 mm in diameter, 1.8 mm in central thickness, with base curvature 6) were obtained having a polycarbonate laminate fused to the convex surface of the lens substrate.
    [00103] In example 1, the L1 laminate was prepared from Macrolon 3158 and also contained 12.5 ppm by weight of Tinopal® OB optical brightener, followed by the polycarbonate substrate Panlite 1250ZT containing 5 ppm by weight of perylene it was overmolded on the L1 laminate.
    [00104] In the comparative examples, the lenses were molded in a single step. The additives were added directly to the polycarbonate (Panlite 1250ZT substrate, still containing 4 ppm of perylene in comparative example 2, 4 ppm of perylene and 25 ppm of Tinopal® OB in comparative example 3).
    [00105] The composition of the prepared lenses is summarized in Table 1: Table 1
    II. Evaluation of optical properties
    [00106] The whiteness index Wi of the prepared lenses was calculated by measuring on a white background with a Hunter UltraScan Pro spectrophotometer the X, Y, Z CIE values, as described in the ASTM E313-73 (1993) and ASTM standards D 1925-70 (1988), through reflection measurements, with the anterior (convex) side of the lens facing the detector and the light entering the front. This way of measuring Wi, from an angle of view of the observer, is the closest to the actual use situation.
    [00107] The light transmission factor in the visible spectrum Tv was measured in transmission mode from the user's angle of view using the spectrophotometer above, with the rear (concave) side of the lens facing the detector and entering the light into the front of the lens.
    [00108] Both Tv and Wi were measured under D65 lighting conditions (daylight).
    [00109] It was chosen to use perylene at a concentration where it absorbs about 9.8% of the radiation having a wavelength of 430 nm (compared to the same lens without the dye), which has been shown to be sufficient to prevent the effects adverse conditions such as age-related atrophic macular degeneration. This absorption was quantified by calculating the light cut (%) at 430 nm for each lens prepared based on the following equation:
    where, T% (ref) is the light transmission (%) at 430 nm of the reference lens of comparative example 1 (which does not include a dye or an optical brightener), and T% is the light transmission (%) at 430 nm of the lens under measurement. III. Results of
    [00110] The optical properties of the lenses mentioned above are summarized in Table 2. Table 2

    [00111] As demonstrated by the illustrative data described above, a system according to the present invention selectively inhibits UV light and blue light, that is, it specifically reduces the light received by the eye in the region of 400 nm-460 nm and almost inhibits the wavelengths below 395 nm, while having an improved white appearance and continues to provide a light transmission of at least about 80% at 430 nm.
    [00112] The whiteness index of the lenses of example 1 is higher than that of the lens of comparative example 3, in which the optical brightener is incorporated into the lens substrate instead of the L1 layer. The light transmission curves of the lenses according to the invention show a higher transmission in deep blue colors, in comparison with the standard lenses of comparative examples 2 and 3.
    [00113] The comparison of comparative examples 2 and 3 reveals that the UV absorbers present in the ophthalmic lens substrate suppress the ability of the optical brightener to emit fluorescence light at a wavelength ranging from 400 to 460 nm. In reality, the incorporation of an optical brightener in the lens substrate of comparative example 2 fails to significantly improve the whiteness index of said lens. Without wishing to be bound by any theory, the inventors believe that this is due to the fact that UV light is absorbed by UV absorbers and is no longer able to trigger the fluorescence emission of the optical brightener when present in the same layer as the UV absorber.
    [00114] As can be seen in figures 1-4, all lenses, except the one without any dye incorporated in it (comparative example 1), have similar levels of blue light cuts of ca. 10% at 430 nm, in the presence or absence of an optical brightener. The cut-off of the UV wavelength, as defined by the wavelength below which light transmission is less than 10%, varies from 390-395 nm in all evaluated lenses (see figures 1-4), due to the presence of UV absorbers on the substrate of the polycarbonate lens.
    权利要求:
    Claims (15)
    [0001]
    1. Transparent optical article characterized by the fact that it comprises a thermoplastic substrate and: - at least one dye A that inhibits, at least partially, light having a wavelength ranging from 400 to 460 nm, preferably from 420 to 450 nm , and - at least one optical brightener B to counterbalance, at least partially, the color imparted to the transparent optical article by dye A, wherein said at least one optical brightener B emits fluorescence light at a wavelength that will from 400 to 460 nm, preferably from 420 to 450 nm, and is incorporated in at least one L1 layer fused or bonded to the thermoplastic substrate, and wherein said dye A and said optical brightener B are different from each other.
    [0002]
    2. Transparent optical article according to claim 1, characterized by the fact that said dye A is incorporated in the thermoplastic substrate and / or in the L1 layer and / or in at least one L2 layer coated on the thermoplastic substrate which is different from layer L1.
    [0003]
    Transparent optical article according to claim 2, characterized in that said dye A is incorporated in layer L2 and layer L2 is interspersed between layer L1 and the thermoplastic substrate.
    [0004]
    Transparent optical article according to any one of the preceding claims, characterized by the fact that said layer L1 has a thickness less than or equal to 2 mm, preferably less than or equal to 1 mm.
    [0005]
    5. Transparent optical article according to any one of the preceding claims, characterized by the fact that it is further defined as having a relative light transmission factor in the visible spectrum of Tv above 80%, more preferably above 85%.
    [0006]
    6. Transparent optical article according to any of the preceding claims, characterized by the fact that dye A is chosen from the families of perylene, coumarin, porphyrin, acridine, indolenine and indole-2-ylidene.
    [0007]
    7. Transparent optical article according to any of the preceding claims, characterized by the fact that optical brightener B is chosen from stilbenes, carbostirils, coumarins, 1,3-diphenyl-2-pyrazolines, naphthalimides and benzoxazoles, preferably from bis-benzoxazoles, phenylcoumarins, methylcoumarins and bis- (styryl) biphenyls.
    [0008]
    Transparent optical article according to any one of the preceding claims, characterized in that said at least one dye A inhibits from 1 to 50% of the light having a wavelength ranging from 420 to 450 nm.
    [0009]
    Transparent optical article according to any one of the preceding claims, characterized by the fact that dye A is incorporated in the thermoplastic substrate in an amount less than 50 ppm relative to the weight of said thermoplastic substrate, preferably less than or equal to 5 ppm.
    [0010]
    Transparent optical article according to any one of claims 2 to 9, characterized in that dye A is incorporated in layer L1 in an amount less than 5000 ppm relative to the weight of said layer, preferably less than 500 ppm, or it is incorporated in layer L2 in an amount of less than 5000 ppm relative to the weight of said layer, preferably less than 500 ppm.
    [0011]
    Transparent optical article according to any one of the preceding claims, characterized in that the optical brightener B is incorporated in layer L1 in an amount of less than 200 ppm relative to the weight of said layer, preferably less than 50 ppm.
    [0012]
    12. Transparent optical article according to any of the preceding claims, characterized by the fact that it is further defined as having a yellowing index Yi of less than 10, preferably less than 5.
    [0013]
    13. Transparent optical article according to any of the preceding claims, characterized by the fact that it is still defined as having a whiteness index Wi greater than 40.
    [0014]
    14. Transparent optical article according to any one of the preceding claims, characterized in that it is additionally defined as an optical lens, preferably an ophthalmic lens, having front and rear main surfaces.
    [0015]
    Transparent optical article according to claim 14, characterized in that said dye A is incorporated into the thermoplastic substrate and said optical brightener B is incorporated into said at least one L1 layer, which is formed on the front main surface of the lens.
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    同族专利:
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    AU2013409186A1|2016-07-07|
    WO2015097492A1|2015-07-02|
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    法律状态:
    2018-08-14| B25A| Requested transfer of rights approved|Owner name: ESSILOR INTERNATIONAL (FR) |
    2020-07-28| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-12-08| B09A| Decision: intention to grant|
    2021-02-23| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/12/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/IB2013/003002|WO2015097492A1|2013-12-23|2013-12-23|Transparent optical article having a reduced yellowness appearance|
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