WO2014199103A1 - Article revêtu d'une couche de nature silico-organique améliorant les performances d'un revêtement externe - Google Patents
Article revêtu d'une couche de nature silico-organique améliorant les performances d'un revêtement externe Download PDFInfo
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- WO2014199103A1 WO2014199103A1 PCT/FR2014/051463 FR2014051463W WO2014199103A1 WO 2014199103 A1 WO2014199103 A1 WO 2014199103A1 FR 2014051463 W FR2014051463 W FR 2014051463W WO 2014199103 A1 WO2014199103 A1 WO 2014199103A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/02—Lenses; Lens systems ; Methods of designing lenses
- G02C7/022—Ophthalmic lenses having special refractive features achieved by special materials or material structures
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/76—Hydrophobic and oleophobic coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
- C03C2217/948—Layers comprising indium tin oxide [ITO]
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C2202/00—Generic optical aspects applicable to one or more of the subgroups of G02C7/00
- G02C2202/16—Laminated or compound lenses
Definitions
- the present invention generally relates to an article, preferably an optical article, in particular an ophthalmic lens, having an outer coating, preferably an anti-fouling coating, the performance of which is improved by the presence of a sub-layer. and a process for preparing such an article.
- the article further has improved thermomechanical properties and a limited ability to develop cosmetic defects over time.
- Optical articles most often include an outer layer that modifies the surface energy, for example a hydrophobic and / or oleophobic antifouling coating, well known in the art and generally associated with anti-reflective coatings. It is most often fluorosilane type materials, which reduce the surface energy to prevent the adhesion of greasy soils that it is easier to remove.
- an outer layer that modifies the surface energy for example a hydrophobic and / or oleophobic antifouling coating, well known in the art and generally associated with anti-reflective coatings. It is most often fluorosilane type materials, which reduce the surface energy to prevent the adhesion of greasy soils that it is easier to remove.
- Application PCT / FR 12053092 in the name of the applicant, discloses an article comprising a substrate having at least one major surface coated with a multilayer interference coating, said coating comprising a non-formed layer A from inorganic precursor compounds having a refraction less than or equal to 1, 55, which constitutes: o either the outer layer of the interference coating,
- o is an intermediate layer, directly in contact with the outer layer of the interference coating, this outer layer of the interferential coating being in this second case an additional layer having a refractive index less than or equal to 1, 55, and said layer A having been obtained by deposition, under an ion beam, of activated species derived from at least one precursor compound C in gaseous form of silico-organic nature such as octamethylcyclotetrasiloxane.
- the layer A constitutes the outer layer of the interference coating
- the anti-fouling coating deposited directly on this layer A has insufficient performance.
- Depositing an additional layer, typically a layer of silica, between the layer A and the antifouling coating improves the performance of the antifouling coating but complicates the deposition process but slightly reduces the scratch resistance and the properties of the antifouling coating. adhesion with respect to the previous embodiment.
- the organic layer A can provide, it would be desirable to be able to improve the performance of the outer coating, particularly an antifouling coating, without having to interpose an additional layer between the layer A and this outer coating.
- the use of ion-deposited organic layers A can cause on certain substrates the gradual appearance of whitish and translucent cosmetic defects, in the form of points and lines extending over the entire surface of the glasses, which are visible under certain lighting conditions (arc lamp and tensioscope).
- the appearance of cosmetic defects on the optical article after its preparation prevents its marketing. Depending on the substrates, these defects are initially present or develop after a period of time ranging from a few days to a few months, during the wearing of ophthalmic lenses.
- US Pat. No. 6,919,134 describes an optical article comprising an antireflection coating comprising at least one so-called “hybrid” layer obtained by co-evaporation of an organic compound and an inorganic compound, which gives it better adhesion and better strength. thermal and better resistance to abrasion.
- the antireflection coating preferably comprises two "hybrid" layers in internal and external position. These layers are generally deposited by ion-assisted co-evaporation typically of silica and a modified silicone oil.
- JP 2007-078780 discloses a spectacle lens comprising a multilayer antireflection coating, the outer layer of which is a layer of low refractive index called "organic". This layer is deposited by liquid means (by centrifugation or soaking), while the inorganic layers of the antireflection coating are deposited by vacuum deposition under ionic assistance.
- the patent application indicates that such antireflection stack has better heat resistance than an antireflection coating composed exclusively of inorganic layers.
- Said "organic” layer preferably comprises a mixture of silica particles and an organosilane binder such as ⁇ -glycidoxypropyltrimethoxysilane.
- the application JP 05-323103 describes the incorporation of a fluorinated organic compound in the last layer of a multilayer optical stack, comprising layers of SiO 2 and TiO 2 , with a view to rendering it hydrophobic and thus minimizing the change in its optical characteristics caused by the absorption of water.
- the fluorinated layer is obtained by vapor deposition of the material constituting the layer in an atmosphere composed of the fluorinated precursor, which may be tetrafluoroethylene or a fluoroalkyl silane.
- the glass when cutting and mounting a glass at the optician, the glass undergoes mechanical deformations that can cause cracks in mineral interferential coatings, especially when the operation is not conducted carefully. Similarly, temperature stresses (heating of the frame) can cause cracks in the interference coating. Depending on the number and size of the cracks, these can interfere with the view for the wearer and prevent the marketing of the glass. In addition, during the wearing of treated organic glasses, scratches may appear. In mineral interferential coatings, some scratches cause cracking, making the scratches more visible due to light scattering.
- another objective of the invention is to obtain a coating, in particular an interference coating, and in particular an anti-reflective coating, having improved thermomechanical properties, while retaining good adhesion properties, and which, moreover, does not develop not (or almost no) during the time of cosmetic defects.
- the invention relates to articles having an improved critical temperature, that is to say having a good resistance to cracking when they are subjected to a rise in temperature.
- this layer is formed by deposition under an ion beam, of activated species, in gaseous form, preferably obtained exclusively from precursor materials of organic nature containing at least one hydrolysable silicon-group link, preferably at least one hydrogen-silicon bond.
- said compound C being neither tetramethyldisiloxane, nor tetraethoxysilane, nor vinylmethyldiethoxysilane, nor hexamethylcyclotrisilazane, and said layer A does not being not formed from inorganic precursor compounds.
- FIG. 1 is a schematic representation of the deformation experienced by the glass and the manner in which this deformation D is measured during the curvature resistance test described. partly experimental.
- the term "depositing a layer or coating on the article” means that a layer or coating is deposited on the exposed surface (exposed ) of the outer coating of the article, that is to say its coating furthest from the substrate.
- a coating that is "on” a substrate or that has been “deposited” on a substrate is defined as a coating that (i) is positioned above the substrate, (ii) is not necessarily in contact with the substrate (although preferentially, it is), that is to say one or more intermediate coatings may be disposed between the substrate and the coating in question, and (iii) does not necessarily cover the substrate completely (although it preferably covers it).
- a layer 1 is located under a layer 2"
- the layer 2 is further away from the substrate than the layer 1.
- the article prepared according to the invention comprises a substrate, preferably transparent, having main front and rear faces, at least one of said main faces comprising a layer A, preferably the two main faces.
- rear face (generally concave) of the substrate is meant the face which, when using the article, is closest to the eye of the wearer.
- front face (generally convex) of the substrate means the face which, when using the article, is furthest from the eye of the wearer.
- the article according to the invention may be any article, such as a screen, a glazing, protective glasses that can be used in particular in a working environment, a mirror, or an article used in electronics, it preferably constitutes a optical article, better an optical lens, and even better an ophthalmic lens, for spectacles, or an optical or ophthalmic lens blank such as a semi-finished optical lens, in particular a spectacle lens.
- the lens may be a polarized, colored lens or a photochromic lens.
- the ophthalmic lens according to the invention has a high transmission.
- the layer A according to the invention may be formed on at least one of the main faces of a bare substrate, that is to say uncoated, or on at least one of the main faces of a substrate already coated with one or more functional coatings.
- the surface of said substrate, optionally coated, is subjected to a physical activation treatment or chemical, intended to increase the adhesion of the layer A.
- This pretreatment is generally conducted under vacuum. It can be a bombardment with energy and / or reactive species, for example an ion beam ("Ion Pre-Cleaning" or "IPC") or an electron beam, a discharge treatment corona, by effluvage, a UV treatment, or vacuum plasma treatment, usually an oxygen or argon plasma. It can also be an acidic or basic surface treatment and / or by solvents (water or organic solvent). Many of these treatments can be combined. Thanks to these cleaning treatments, the cleanliness and reactivity of the surface of the substrate are optimized.
- the interference coating may be any interferential coating conventionally used in the field of optics, in particular ophthalmic optics, except that it comprises an outer layer A formed by deposition, under a beam of ions of species activated from an organic derivative, preferably a silicon hydride, in gaseous form.
- the interference coating may be, without limitation, an antireflection coating, a reflective coating (mirror), an infrared filter or an ultraviolet filter, preferably an antireflection coating.
- An antireflective coating is defined as a coating deposited on the surface of an article that improves the anti-reflective properties of the final article. It reduces the reflection of light at the article-air interface over a relatively large portion of the visible spectrum.
- the H1 layers are conventional high refractive index layers well known in the art. They generally comprise one or more mineral oxides such as, without limitation, zirconia (ZrO 2 ), titanium oxide (TiO 2 ), tantalum pentoxide (Ta 2 O 5 ), neodymium oxide (Nd 2 0 5 ), hafnium oxide (HfO 2 ), praseodymium oxide (Pr 2 O 3 ), praseodymium titanate (PrTiO 3 ), La 3 O 3 , Nb 2 O 5 , Y 2 0 3 , indium oxide In 2 0 3 , or tin oxide SnO 2 .
- Preferred materials are Ti0 2, Ta 2 0 5, PrTi0 3, Zr0 2, Sn0 2, ln 2 0 3 and mixtures thereof.
- all the layers of low refractive index of the interference coating according to the invention are of inorganic nature with the exception of the layer A (that is to say that the other layers of low refractive index of the interferential coating do not contain preferably no organic compound).
- Sub-layer of the interference coating means a coating of relatively large thickness, used for the purpose of improving the resistance to abrasion and / or scratching of said coating and / or promoting its adhesion to the substrate or coating underlying.
- the underlayer according to the invention may be chosen from the sub-layers described in application WO 2010/109154.
- the underlayer has a thickness of 100 to 200 nm. It is preferably of exclusively inorganic nature and preferably consists of SiO 2 silica.
- the article of the invention can be made antistatic by incorporating into the interference coating at least one electrically conductive layer.
- antistatic is meant the property of not retaining and / or developing an appreciable electrostatic charge.
- An article is generally considered to have acceptable antistatic properties when it does not attract and fix dust and small particles after one of its surfaces has been rubbed with a suitable cloth.
- compound C is neither 1,2,3,4,5,6-hexamethylcyclotrisilazane nor 2,2,4,4,6,6-hexamethylcyclotrisilazane.
- the definition of the groups -NR R 2 and -N (R 3 ) -Si indicated above naturally excludes compounds such as hexamethyldisilazane.
- the ions can be subject, if necessary, to a neutralization before the exit of the ion gun. In this case, the bombing will still be considered ionic.
- the ion bombardment causes atomic rearrangement and densification in the layer being deposited, which allows it to be compacted while it is being formed.
- the surface to be treated is preferably bombarded with ions, with a current density generally between 20 and 1000 ⁇ / cm 2 , preferably between 30 and 500 ⁇ / cm 2. preferably between 30 and 200 ⁇ / cm 2 on the activated surface and generally under a residual pressure in the vacuum chamber which may vary from 6.10 -5 mbar to 2.10 -4 mbar, preferably from 8.10 -5 mbar to 2.10 -4 mbar.
- An argon and / or oxygen ion beam is preferably used:
- the molar ratio Ar / O 2 is preferably ⁇ 1, better ⁇ 0.75 and even better ⁇ 0.5 This ratio can be controlled by adjusting the gas flow rates in the ion gun
- the argon flow rate preferably varies from 0 to 30 sccm
- the flow rate of oxygen 0 2 preferably varies from 5 to 30 sccm, and is even larger than the flow rate of the precursor compound of the layer A is high.
- the atomic percentage of carbon atoms in layer A preferably varies from 8 to 25%, more preferably from 15 to 25%.
- the atomic percentage of hydrogen atoms in layer A preferably varies from 8 to 40%, more preferably from 10 to 20%.
- the atomic percentage of silicon atoms in layer A preferably varies from 5 to 30%, more preferably from 15 to 25%.
- the atomic percentage of oxygen atoms in layer A preferably varies from 20 to 60%, more preferably from 35 to 45%.
- the most common members belonging to this group are tetra-, penta- and hexa- alkylcyclotetrasiloxanes, preferably tetra-, penta- and hexamethylcyclotetrasiloxanes,
- the compound C is a linear alkylhydrosiloxane, better a linear methylhydrosiloxane such as for example 1, 1, 1, 3,5,7,7,7-octamethyltetrasiloxane, 1, 1, 1, 3,5,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane.
- Non-limiting examples of organic precursor compounds of layer A, cyclic or non-cyclic are the following compounds 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS of formula (1)), 2,4,6,8 ⁇ -tetramethylcyclotetrasiloxane, 2,4,6,8-tetraphenylcyclotetrasiloxane, 2,4,6,8-tetraoctylcyclotetrasiloxane, 2,2,4,6,6,8-hexamethylcyclotetrasiloxane, 2,4,6-trimethylcyclotrisiloxane, cyclotetrasiloxane, the following compounds 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS of formula (1)), 2,4,6,8 ⁇ -tetramethylcyclotetrasiloxane, 2,4,6,8-tetraphenylcyclotetrasiloxane, 2,4,6,8-tetraoctylcyclotetrasiloxan
- the precursor compound of the layer A is preferably introduced into the vacuum chamber in which the preparation of the articles according to the invention in gaseous form is carried out, by controlling its flow rate. This means that it is preferably not vaporized inside the vacuum chamber.
- the precursor compound supply of the layer A is at a distance from the exit of the ion gun, preferably ranging from 30 to 50 cm.
- the process for forming the interference coating according to the invention is therefore much simpler and less expensive than the processes for co-evaporation of an organic compound and an inorganic compound, such as that described in US Pat. No. 6,919,134.
- the co-evaporation processes are very difficult to implement, and difficult to control because of reproducibility problems.
- the respective amounts of organic and inorganic compounds present in the deposited layer vary greatly from one manipulation to another.
- the stress of layer A is zero or negative. In the latter case, the layer is in compression.
- This compressive stress preferably varies from 0 to -500 MPa, more preferably from -20 to -500 MPa, more preferably from -50 to -500 MPa.
- the optimum compressive stress ranges from -150 to -400 MPa and better from -200 to -400 MPa. It is measured at a temperature of 20 ° C and 50% relative humidity as described below. It is the filing conditions of the invention that make it possible to achieve this constraint.
- the principle of stress measurement is based on the monitoring of the deformation of a thin substrate.
- d f is the thickness of the film (m)
- E s is the Young's modulus of the substrate (Pa)
- v s is the Poisson's ratio of the substrate
- R 1 is the measured radius of curvature of the substrate prior to deposition
- R 2 is the measured radius of curvature of the substrate coated with the film after deposition.
- Curvature is measured using a Tencor FLX 2900 (Flexus).
- a Class Nia laser with 4 milliwatts (mW) power at 670 nm is used for the measurement.
- the device allows measurement of internal stresses as a function of time or temperature (maximum temperature of 900 Q C).
- the stress of the interference coating generally varies from 0 to -400 MPa, preferably from -50 to -300 MPa, better from -80 to -250 MPa, and more preferably from -100 to -200 MPa.
- the critical temperature of a coated article according to the invention is preferably greater than or equal to 80 ° C, more preferably greater than or equal to 90 ° C and more preferably greater than or equal to 100 ° C.
- the cretal temperature of an article or a coating is defined as that from which the appearance of cracks in the stack present on the surface of the substrate is observed, which reflects a degradation of the coating.
- This high critical temperature is due to the presence of the layer A on the surface of the article, as demonstrated in the experimental part.
- the inventors believe that, in addition to the nature of the layer, the use of layers A, by making it possible to increase the compressive stress of the entire stack, improves the critical temperature of the article.
- the interference coating of the invention is an antireflection coating comprising, in the order of deposition on the surface of the optionally coated substrate, a layer of Zr0 2 , generally 10 to 40 nm thick and preferably from 15 to 35 nm, a layer of Si0 2, generally from 10 to 40 nm thick and preferably 15 to 35 nm, a layer of Zr0 2 or Ti0 2, generally from 40 to 150 nm thick, preferably from 50 to 120 nm, an ITO layer, generally from 1 to 15 nm thick and preferably from 2 to 10 nm, and a layer A according to the invention, generally from 50 to 150 nm thick and preferentially from 60 to 100 nm.
- a layer of Zr0 2 generally 10 to 40 nm thick and preferably from 15 to 35 nm
- a layer of Si0 2 generally from 10 to 40 nm thick and preferably 15 to 35 nm
- a layer of Zr0 2 or Ti0 2 generally from 40 to 150 nm thick,
- the main surface of the substrate is coated with one or more functional coatings prior to the deposition of the layer A or the multilayer coating comprising the layer A as the outer layer.
- These functional coatings conventionally used in optics may be, without limitation, a primer layer improving the impact resistance and / or the adhesion of the subsequent layers in the final product, an abrasion-resistant and / or anti-scratch coating, a coating polarized, a photochromic coating or a colored coating, in particular a primer layer coated with an abrasion-resistant and / or scratch-resistant layer.
- a primer layer improving the impact resistance and / or the adhesion of the subsequent layers in the final product
- an abrasion-resistant and / or anti-scratch coating a coating polarized
- a photochromic coating or a colored coating in particular a primer layer coated with an abrasion-resistant and / or scratch-resistant layer.
- the article according to the invention comprises a hydrophobic external coating B, directly deposited on the layer A, capable of modifying its surface properties, such as a hydrophobic and / or oleophobic coating (synonymous with a top coat or anti-fouling coating in the present invention). request).
- Its thickness is generally less than or equal to 10 nm, preferably from 1 to 10 nm, more preferably from 1 to 5 nm. It is described in applications WO 2009/047426.
- the outer hydrophobic coating B may be a monolayer or multilayer coating, preferably monolayer. In the case where the coating B comprises several layers, the layer A is in direct contact with the inner layer of the coating B, that is to say the layer of the coating B closest to the substrate in the stacking order. .
- fluorosilane or fluorosilazane precursor preferably comprising at least two hydrolyzable groups per molecule.
- the precursor fluorosilanes preferentially contain fluoropolyether groups and better still perfluoropolyether groups.
- fluorosilanes are well known and are described, inter alia, in patents US 5,081,192, US 5,763,061, US 6,183,872, US 5,739,639, US 5,922,787, US 6,337,235, US 6,277,485 and EP 0933377.
- Such compounds are capable of to undergo, when deposited on a surface, polymerization reactions and / or crosslinking, directly or after hydrolysis.
- compositions for preparing hydrophobic and / or oleophobic coatings are the compositions KY130® (corresponding to the formula of the patent JP 2005- 187936) and KP 801 M® marketed by Shin-Etsu Chemical, and the composition OPTOOL DSX® (a fluorinated resin comprising perfluoropropylene groups corresponding to the formula of US Pat. No. 6,183,872) marketed by Daikin Industries.
- the OPTOOL DSX® composition is the preferred antifouling coating composition.
- an article according to the invention comprises a substrate successively coated with a layer of adhesion and / or shockproof primer, with an anti-abrasion and / or anti-scratch coating, with an interference coating according to the invention, optionally antistatic, having the layer A as an outer layer, and a hydrophobic and / or oleophobic coating.
- precursor compounds C according to the invention rather than precursor compounds such as OMCTS, hexamethyldisiloxane, decamethyltetrasiloxane or decamethylcyclopentasiloxane allowed hydrophobic outer coating B to exhibit satisfactory performance, although that the organic layer A is in direct contact with said hydrophobic external coating B.
- Si-X bonds (X having the meaning indicated above) in the precursor compound C is decisive for obtaining this result, these Si-X bonds. being less stable than the Si-C bonds, in particular more subject to oxidation and hydrolysis in the presence of oxygen and the water present in the ambient air. It is assumed that at least part of the molecular structure of precursor C would be kept intact during the deposition process of layer A, because of the particular method used for the deposition of this precursor. As a result, constitutive structures of the precursor molecule would persist in layer A, particularly at the surface of the deposited layer.
- the layers A obtained from the precursors C according to the invention would comprise at the surface a certain proportion of pendant reactive bonds Si-X.
- the Si-X bonds exposed to air and the ambient humidity could form Si-OH reactive sites, which favor the attachment of the molecules of the upper layer (generally an antifouling coating).
- organic layers formed under the same conditions from precursors such as OMCTS, hexamethyldisiloxane, decamethyltetrasiloxane or decamethylcyclopentasiloxane would have only pendant Si-alkyl bonds. These groups being hydrophobic and stable, their presence does not a priori favor the hydrolysis and condensation reactions necessary for the grafting of the precursor molecules of the subsequent coating.
- precursor compounds C according to the invention with respect to precursors such as OMCTS, hexamethyldisiloxane, decamethyltetrasiloxane or decamethylcyclopentasiloxane is to obtain stacks that do not contain cosmetic defects for a range of conditions. extended deposit, and those even on stacks more inclined to develop cosmetic defects.
- the layer A constitutes the outer layer of this stack is particularly advantageous because this makes it possible to increase the resistance to abrasion and scratching, and thus decreases in particular the number of scratches that can lead to the appearance of cracks in the interference coating.
- the invention also relates to a method of manufacturing an article as defined above, comprising at least the following steps:
- the articles used in the examples include a 65 mm diameter ORMA ® ESSILOR lens substrate with a power of -2.00 diopters and a thickness of 1.2 mm (except for the evaluation of the possible presence of cosmetic defects). , made on the MR8 thiourethane substrate of Mitsui Toatsu Chemicals Inc. with refractive index 1, 59, all things being equal), coated on its concave side with the shock-proof primer coating and the anti-abrasion and anti-abrasion coating. hard coat disclosed in the experimental part of the application WO 2010/109154, an antireflection coating and the antifouling coating disclosed in the experimental part of the application WO 2010/109154.
- the layers of the antireflection coating were deposited without heating the substrates by vacuum evaporation, possibly, when specified, assisted by oxygen ion beam and possibly argon during the deposition (evaporation source: electron gun).
- the vacuum deposition frame is a Leybold LAB 1 100 + machine equipped with an electron gun for the evaporation of precursor materials, a thermal evaporator, a KRIF ERI 1000 F ion gun (from Kaufman) & Robinson Inc.) for the preliminary phase of preparing the substrate surface with argon ions (IPC), as well as for layer A or ion-assisted layer (IAD) deposits, and a system of liquid introduction, used when the precursor compound of layer A is a liquid under normal conditions of temperature and pressure (case of TMCTS).
- IPC argon ions
- IAD ion-assisted layer
- This system comprises a reservoir containing the liquid precursor compound of the layer A, resistors for heating the reservoir and the tubes connecting the liquid precursor reservoir to the vacuum deposition machine, a flow meter for the steam of the MKS company (MKS1 150C ), brought to a temperature of 30-150 ° C during its use, according to the flow of vaporized precursor, which preferably varies from 10 to 50 sccm.
- the precursor vapor exits a pipe inside the machine, at a distance of about 30 cm from the ion gun. Flow rates of oxygen and possibly argon are introduced inside the ion gun. Preferably, no argon or any other rare gas is introduced into the ion gun.
- the layers A according to the invention are formed by evaporation under ionic bombardment of TMCTS compound.
- the thickness of the deposited layers was monitored in real time using a quartz microbalance. Unless otherwise indicated, the thicknesses mentioned are physical thicknesses. Several samples of each glass were prepared.
- the process for preparing optical articles according to the invention comprises introducing the substrate coated with the primer coating and the anti-abrasion coating defined above into the vacuum deposition chamber, a step of preheating the vaporizer, tubes and steam flowmeter at the chosen temperature ( ⁇ 20 min), a primary pumping step, then secondary pumping for 400 s to obtain a secondary vacuum ( ⁇ 2, 10 ⁇ 5 mbar, pressure read on a Bayard-Alpert gauge), a step of activation of the substrate surface by an argon ion beam (IPC: 1 minute, 100 V, 1 A, the ion gun being stopped at the end of this step) then the evaporation deposition of the following inorganic layers using the electron gun until the desired thickness for each layer is obtained:
- IPC argon ion beam
- the deposition of the layer A on the ITO layer is then carried out as follows.
- the ion gun is then started with argon, oxygen is added in the ion gun, with a programmed flow (20 sccm), the argon flow is cut off, the desired anode current is programmed (3 A) and the compound TMCTS is introduced into the chamber (flow rate programmed at 20 sccm).
- flow rates flow rates: TMCTS: 20 sccm; Ar: 0 sccm, 0 2 : 20 sccm, current 3A).
- the process according to the invention is carried out with oxygen (O 2 ) in the ion gun, in the absence of rare gas introduced into the ion gun.
- TMCTS compound is stopped once the desired thickness is obtained, then the ion gun is extinguished.
- Example 1 a layer of antifouling coating (top coat) based on Optool
- Daikin DSX TM of the order of 5 nm is deposited directly on a layer A 85 nm thick, which is the outer layer of the antireflection coating.
- Comparative Example 1 differs from the stack according to the invention in that layer A is replaced by a layer of silica of the same thickness (85 nm).
- Comparative Example 2 differs from the stack according to the invention in that the layer A is replaced by a layer of the same thickness (85 nm) obtained under the same conditions by ion-bombardment evaporation of the compound OMCTS (octamethylcyclotetrasiloxane, which has no hydrolyzable Si-group linkage) provided by ABCR, in place of the TMCTS compound.
- OMCTS octamethylcyclotetrasiloxane, which has no hydrolyzable Si-group linkage
- Bayer ASTM Bayer Sand
- the critical temperature of the article is measured as indicated in WO 2008/00101 1, 24 hours after the preparation of this article.
- the curvature resistance test evaluates the ability of an article having a curvature to undergo mechanical deformation. This test is performed on an initially spherical glass which has been overflowed to the shape of a rectangle of dimension 50 x 25 mm.
- the solicitation mode of this test is representative of the solicitation at the optician for mounting the glass, that is to say the "compression" of the glass for insertion into a metal frame.
- This test uses an Instron bench to apply controlled deformation to the glass, light-emitting diodes (LEDs) to illuminate the glass, a camera and image analysis software.
- the coated glass is compressed by the Instron bench, by applying forces exerted along the axis of the main length of the overflow glass until cracks perpendicular to the direction of movement in the antireflection coating are detected by analysis of the image in transmission.
- the result of the test is the critical strain D in mm that the glass can undergo before the appearance of cracks, shown in FIG. This test is carried out a month after the preparation of the glasses. The higher the value of the deformation, the better the resistance to mechanical deformation applied.
- the interferential coatings according to the invention have critical strain values ranging from 0.7 to 1.2 mm, better still from 0.8 mm to 1.2 mm and better still from 0.9 to 1. , 2 mm.
- optical articles articles according to the invention or comparative
- an arc lamp high intensity lamp
- tO + 1 week or tO + 1 month the reference time tO corresponding to 1 day after the preparation of the articles.
- atmospheric pressure is meant a pressure of 1.01325 Bar.
- the adhesion test makes it possible to evaluate the adhesion properties of the coating by carrying out a dip treatment in hot water followed by a mechanical surface stress. The higher the result, the better the adhesion.
- the ink test is used to evaluate the performance of the anti-fouling coating. This test consists of drawing a line with the "Magic Ink” marker No. 500 from Teranishi Chemical Industries Ltd, and then evaluating the trace left on the glass. When the ink retracts quickly ( ⁇ 3s) into small droplets, the result is considered to be “compliant”. When the trace is continuous or has continuous intervals, the "non-compliant" result is considered.
- the article according to the invention has an improved critical temperature and a significant improvement in the curvature deformation that it can undergo before the occurrence of cracks compared with that of Comparative Example 1. These improvements are directly attributable to the presence of a layer A in the antireflection stack. It can be seen that it is not necessary for all the layers of the antireflection coating to be layers of organic nature such as layer A to obtain an improvement in the behavior of the product with respect to the thermomechanical stresses.
- the article according to the invention has an anti-fouling coating which is more efficient than that of Comparative Example 2 and as effective as that deposited on a silica layer (Comparative Example 1), as revealed by the ink test, while retaining good mechanical properties.
- Comparative Example 1 silica layer
- the use of other precursors such as hexamethyldisiloxane, decamethyltetrasiloxane or decamethylcyclopentasiloxane, which, like OMCTS, do not have hydrolyzable Si-group bonds leads to antifouling coating performance that is lower than that obtained. using a layer A according to the invention.
- the article according to the invention has a limited ability to develop in time cosmetic defects, while that of Comparative Example 2 has such defects after a relatively short time after preparation.
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Geochemistry & Mineralogy (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Ophthalmology & Optometry (AREA)
- Composite Materials (AREA)
- General Health & Medical Sciences (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Eyeglasses (AREA)
- Physical Vapour Deposition (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (7)
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EP14735625.7A EP3008023B1 (fr) | 2013-06-14 | 2014-06-13 | Article revêtu d'une couche de nature silico-organique améliorant les performances d'un revêtement externe |
BR112015030592-0A BR112015030592B1 (pt) | 2013-06-14 | 2014-06-13 | Artigo revestido com uma camada de natureza sílica orgânica para melhorar os desempenhos de um revestimento externo |
US14/898,425 US10401536B2 (en) | 2013-06-14 | 2014-06-13 | Item coated with a silicon/organic layer improving the performances of an outer coating |
KR1020157034784A KR102315194B1 (ko) | 2013-06-14 | 2014-06-13 | 외부 코팅의 성능을 개선시키는 실리콘/유기층으로 코팅된 물품 |
CN201480033244.8A CN105324343B (zh) | 2013-06-14 | 2014-06-13 | 涂布有改进外涂层性能的硅/有机层的物品 |
CA2915139A CA2915139C (fr) | 2013-06-14 | 2014-06-13 | Article revetu d'une couche de nature silico-organique ameliorant les performances d'un revetement externe |
JP2016518574A JP6751017B2 (ja) | 2013-06-14 | 2014-06-13 | 外側コーティングの性能を改良するケイ素/有機層で被覆された物品 |
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FR1355604A FR3007024A1 (fr) | 2013-06-14 | 2013-06-14 | Article revetu d'une couche de nature silico-organique ameliorant les performances d'un revetement externe |
FR1355604 | 2013-06-14 |
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WO2014199103A1 true WO2014199103A1 (fr) | 2014-12-18 |
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PCT/FR2014/051463 WO2014199103A1 (fr) | 2013-06-14 | 2014-06-13 | Article revêtu d'une couche de nature silico-organique améliorant les performances d'un revêtement externe |
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US (1) | US10401536B2 (fr) |
EP (1) | EP3008023B1 (fr) |
JP (1) | JP6751017B2 (fr) |
CN (1) | CN105324343B (fr) |
BR (1) | BR112015030592B1 (fr) |
CA (1) | CA2915139C (fr) |
FR (1) | FR3007024A1 (fr) |
WO (1) | WO2014199103A1 (fr) |
Cited By (9)
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WO2017021669A1 (fr) * | 2015-08-05 | 2017-02-09 | Essilor International (Compagnie Générale d'Optique) | Article à propriétés d'adhérence optimisées comportant une couche de nature silico-organique |
CN107848877A (zh) * | 2015-08-05 | 2018-03-27 | 依视路国际公司 | 具有改进的热机械特性、包括有机‑无机层的物品 |
US10401536B2 (en) | 2013-06-14 | 2019-09-03 | Essilor International | Item coated with a silicon/organic layer improving the performances of an outer coating |
EP3640687A1 (fr) | 2018-10-18 | 2020-04-22 | Essilor International | Article optique comportant un revêtement interférentiel avec une haute résistance à l'abrasion |
EP3640688A1 (fr) | 2018-10-18 | 2020-04-22 | Essilor International | Article optique comportant un revêtement interférentiel ayant une meilleure résistance à l'abrasion |
US10732324B2 (en) | 2015-08-05 | 2020-08-04 | Essilor International | Method for laminating an interference coating comprising an organic/inorganic layer, and item thus obtained |
EP3693766A1 (fr) | 2019-02-05 | 2020-08-12 | Corporation de L'Ecole Polytechnique de Montreal | Article revêtu d'une couche à faible indice de réfraction basé sur des composés d'organosilicium fluorés |
EP4197761A1 (fr) | 2021-12-16 | 2023-06-21 | Essilor International | Procédé de thermoformage d'un film par rétraction thermique et son laminage sur un article optique |
EP4369062A1 (fr) | 2022-11-14 | 2024-05-15 | Essilor International | Article revêtu d'une couche à faible indice de réfraction à base de composés silsesquioxanes organiques |
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FR3051000B1 (fr) * | 2016-05-09 | 2018-06-01 | Corporation De L'ecole Polytechnique De Montreal | Article comportant une couche de nature organique-inorganique de bas indice de refraction obtenue par depot a angle oblique |
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CN113684449B (zh) * | 2021-08-06 | 2023-09-08 | 南京波长光电科技股份有限公司 | 一种低吸收高功率光纤激光增透膜及其制备方法 |
WO2024116961A1 (fr) * | 2022-12-02 | 2024-06-06 | 株式会社ニコン・エシロール | Procédé de fabrication d'article optique |
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Cited By (19)
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US10401536B2 (en) | 2013-06-14 | 2019-09-03 | Essilor International | Item coated with a silicon/organic layer improving the performances of an outer coating |
US10732324B2 (en) | 2015-08-05 | 2020-08-04 | Essilor International | Method for laminating an interference coating comprising an organic/inorganic layer, and item thus obtained |
FR3039827A1 (fr) * | 2015-08-05 | 2017-02-10 | Essilor Int | Article a proprietes d'adherence optimisees comportant une couche de nature silico-organique |
CN107848877A (zh) * | 2015-08-05 | 2018-03-27 | 依视路国际公司 | 具有改进的热机械特性、包括有机‑无机层的物品 |
CN107923995A (zh) * | 2015-08-05 | 2018-04-17 | 依视路国际公司 | 具有优化的粘合特性并且包括硅有机层的物品 |
CN107923995B (zh) * | 2015-08-05 | 2020-01-17 | 依视路国际公司 | 具有优化的粘合特性并且包括硅有机层的物品 |
US11707921B2 (en) | 2015-08-05 | 2023-07-25 | Essilor International | Item having improved thermomechanical properties, comprising an organic-inorganic layer |
CN107848877B (zh) * | 2015-08-05 | 2022-07-15 | 依视路国际公司 | 具有改进的热机械特性、包括有机-无机层的物品 |
WO2017021669A1 (fr) * | 2015-08-05 | 2017-02-09 | Essilor International (Compagnie Générale d'Optique) | Article à propriétés d'adhérence optimisées comportant une couche de nature silico-organique |
WO2020079241A1 (fr) | 2018-10-18 | 2020-04-23 | Essilor International | Article optique doté d'un revêtement interférentiel ayant une haute résistance à l'abrasion |
WO2020079197A1 (fr) | 2018-10-18 | 2020-04-23 | Essilor International | Article optique pourvu d'un revêtement interférentiel doué d'une résistance à l'abrasion améliorée |
EP3640688A1 (fr) | 2018-10-18 | 2020-04-22 | Essilor International | Article optique comportant un revêtement interférentiel ayant une meilleure résistance à l'abrasion |
EP3640687A1 (fr) | 2018-10-18 | 2020-04-22 | Essilor International | Article optique comportant un revêtement interférentiel avec une haute résistance à l'abrasion |
EP3693766A1 (fr) | 2019-02-05 | 2020-08-12 | Corporation de L'Ecole Polytechnique de Montreal | Article revêtu d'une couche à faible indice de réfraction basé sur des composés d'organosilicium fluorés |
WO2020161128A1 (fr) | 2019-02-05 | 2020-08-13 | Corporation De L'ecole Polytechnique De Montreal | Article revêtu d'une couche à faible indice de réfraction à base de composés organosiliciques fluorés |
EP4197761A1 (fr) | 2021-12-16 | 2023-06-21 | Essilor International | Procédé de thermoformage d'un film par rétraction thermique et son laminage sur un article optique |
WO2023110887A1 (fr) | 2021-12-16 | 2023-06-22 | Essilor International | Procédé pour le thermoformage d'un film par retrait thermique et lamination de celui-ci sur un article optique |
EP4369062A1 (fr) | 2022-11-14 | 2024-05-15 | Essilor International | Article revêtu d'une couche à faible indice de réfraction à base de composés silsesquioxanes organiques |
WO2024104972A1 (fr) | 2022-11-14 | 2024-05-23 | Essilor International | Article revêtu d'une couche à faible indice de réfraction à base de composés silsesquioxane organiques |
Also Published As
Publication number | Publication date |
---|---|
CN105324343B (zh) | 2017-12-29 |
JP6751017B2 (ja) | 2020-09-02 |
EP3008023A1 (fr) | 2016-04-20 |
JP2016521871A (ja) | 2016-07-25 |
BR112015030592A2 (pt) | 2017-07-25 |
CN105324343A (zh) | 2016-02-10 |
FR3007024A1 (fr) | 2014-12-19 |
CA2915139A1 (fr) | 2014-12-18 |
US10401536B2 (en) | 2019-09-03 |
US20160139304A1 (en) | 2016-05-19 |
BR112015030592B1 (pt) | 2021-11-03 |
EP3008023B1 (fr) | 2017-08-09 |
CA2915139C (fr) | 2021-11-23 |
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