EP1979281A1 - Procedes de fabrication d'un article revetu d'un film photochrome et leur application en optique ophtalmique - Google Patents
Procedes de fabrication d'un article revetu d'un film photochrome et leur application en optique ophtalmiqueInfo
- Publication number
- EP1979281A1 EP1979281A1 EP07731546A EP07731546A EP1979281A1 EP 1979281 A1 EP1979281 A1 EP 1979281A1 EP 07731546 A EP07731546 A EP 07731546A EP 07731546 A EP07731546 A EP 07731546A EP 1979281 A1 EP1979281 A1 EP 1979281A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- film
- agent
- photochromic
- hydrophobic
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/23—Photochromic filters
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
- C03C1/008—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route for the production of films or 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
- 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
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
-
- 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
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
Definitions
- the present invention generally relates to methods of manufacturing an article, in particular of plastic, coated with an optionally mesostructured photochromic sol-gel film and the coated articles thus obtained. These articles are advantageously used in the field of optics.
- the present invention relates to a method of manufacturing a transparent article, preferably of a plastics material, such as an optical or ophthalmic lens or lens blank, coated with a photochromic film.
- the mesoporous materials are defined as solids comprising in their structure pores having a size ranging from 2 to 50 nm, called mesopores. This pore size is intermediate between that of macropores (size> 50 nm) and that of micropores of zeolite type materials (size ⁇ 2 nm).
- Mesopores can be empty, ie filled with air, or only partially empty. Mesopores are usually randomly distributed in the structure, with a wide size distribution. Mesoporous materials and their preparation have been widely described in the literature, notably in Science 1983, 220, 365371 or The Journal of Chemical Society, Faraday Transactions 1985, 81, 545-548.
- structured materials are defined as materials having an organized structure, characterized more specifically by the existence of at least one diffraction peak in an X-ray diffraction pattern or neutrons.
- the diffraction peaks observed in these types of diagrams may be associated with the repetition of a characteristic distance of the material, called the spatial repetition period of the structured system.
- a mesostructured material is defined as a structured material having a spatial repetition period ranging from 2 to 50 nm.
- Structured mesoporous (or ordered mesoporous) materials are a particular class of mesostructured materials. They are mesoporous materials with an organized spatial arrangement of the mesopores present in their structure, which results in a period of spatial repetition.
- the conventional process for preparing mesoporous films, optionally structured mesoporous consists in preparing a low-polymerized sol of an inorganic material such as silica, from a precursor such as a tetraalkoxysilane, in particular the tetraethoxysilane (TEOS), this soil also containing water, a generally polar organic solvent such as ethanol and a pore-forming agent, most often in acidic medium.
- TEOS tetraalkoxysilane
- blowing agent is an amphiphilic agent, for example a surfactant, it acts as a structuring agent and generally leads to structured materials, which will now be explained.
- the concentration of surfactant in the solution is before the deposition much lower than the critical micelle concentration.
- This soil is then deposited on a support.
- the organic solvent evaporates, which enriches the film in water, surfactant and silica, then the critical micellar concentration is reached.
- the solvent medium being very polar, the surfactant molecules cluster into clusters, forming micelles with their polar heads towards the solvent.
- the inorganic network for example silica
- the silica which is also very polar, forms a matrix around the micelles rather than around the individual molecules of su rfa being and thus composite species consisting of organic micelles coated with mineral precursors are obtained.
- the network grows and traps or encapsulates the micelles inside the solid structure.
- the micelles eventually change shape and self-organize in more or less ordered structures, for example in hexagonal, cubic or lamellar network until the drying of the film.
- the final arrangement of the mineral matrix obtained is governed by the shape of the micelles generated by the amphiphilic molecules used.
- the pore size in the final material depends on the size of the pore-forming agent that is trapped or encapsulated within the silica network.
- a surfactant surfactant
- the pore size in the solid is relatively large because the silica network is built around micelles, that is to say, colloidal particles, formed by the surfactant.
- the micelles are larger in size than their constituents, so that the use of a surfactant as a blowing agent generally produces a mesoporous material.
- blowing agent When the blowing agent is not an amphiphilic agent, it does not form micelles under the conditions of the reaction and does not lead to structured materials.
- this pore-forming agent can optionally be removed from the material, in which case a mesoporous material is obtained.
- a material may be described as mesoporous when the pore-producing agent used for its preparation has been at least partially removed from at least a part of this material, that is to say at least some of this material contains at least partially empty mesopores.
- the removal of the blowing agent can be done by calcination (heating at a temperature generally of the order of 400 ° C.), or by more moderate methods (extraction with solvents, with a supercritical fluid, UV / ozone, plasma).
- silica In the place of silica, it is possible to use other inorganic materials, for example metal or metalloid precursor oxides, for example based on titanium, niobium or aluminum.
- metal or metalloid precursor oxides for example based on titanium, niobium or aluminum.
- the mesoporous films described in the state of the art generally have high porosity levels, greater than 40% by volume, these pores being filled with air, and possess the properties which result therefrom, in particular a refractive index and a low dielectric coefficient.
- the mesoporous materials can serve as hosts to a wide variety of guest chemical species with particular intrinsic properties, a faculty that can be used to impart particular optical, electrical, magnetic, chemical or catalytic properties to the material depending upon the nature of the material. guest species selected.
- the present application is concerned with the incorporation of photochromic compounds into the pores of such materials.
- photochromic films During the preparation of photochromic films, it is therefore necessary to optimize the mechanical properties of the films while ensuring the photochromic environment conducive to coloring / discoloration. To meet these requirements, various solutions are already known. It is first possible to incorporate the photochromic into an organic polymer. It is also possible to incorporate the photochromic into a "dense" sol-gel film. Typically, a sol containing no pore-forming agent is prepared, most often by hydrolysis and simultaneous condensation of different precursors. To this soil is added the photochrome, before proceeding to the deposit of the film.
- Soft in which the photochromic is placed
- the soft areas provide an environment favorable to the operation of the photochromic, that is to say to the smooth running of the opening / closing cycles. Fast staining and fading kinetics are obtained, comparable to those observed in solution. In this case, the performances of the system are limited solely by the characteristics intrinsic to the chosen photochromic molecule, which behaves as in a solvent medium.
- mesoporous silica structures whether or not containing a surfactant-type pore-forming agent, have good mechanical strength.
- Two synthesis techniques have been used in the state of the art to obtain mesoporous or mesostructured photochromic films. These two methods, called impregnation and direct synthesis, will now be presented.
- the impregnation technique consists in impregnating a mesoporous film with a solution containing a photochrome and is described in particular in "Photochromism in spiropyran impregnated fluorinated mesoporous organosilicate films", Bae, JY; Jung, JI; Bae, B.-SJ Mater. Res. 2004, 19, 2503-2509.
- a film having a hydrophobic matrix is prepared by simultaneous acid hydrolysis (HCl) and condensation of TEOS (Si (OEt) 4 , silica precursor) and a trialkoxy silane having a silicon-bonded fluorinated aliphatic chain, presence of the surfactant CTAC (cetyltrimethylammonium chloride), the two silanes being used in a ratio of 9: 1.
- HCl acid hydrolysis
- OEt silica precursor
- a trialkoxy silane having a silicon-bonded fluorinated aliphatic chain presence of the surfactant CTAC (cetyltrimethylammonium chloride)
- CTAC cetyltrimethylammonium chloride
- WO 02/41043 which contemplate the preparation of a silica matrix film (TMOS or TEOS precursor) or based on a transition metal, mesostructured by the CTAC surfactant or a block copolymer type surfactant. This can be removed by calcination at 550 ° C. or extraction at low temperature ( ⁇ 110 ° C.) with a solvent (ethanol) or a supercritical fluid.
- a photochromic spiropyran type for example, is then incorporated by impregnation, providing a structured mesoporous photochromic film having good mechanical properties.
- the surfactant is not not removed from the film structure before impregnation with a photochromic solution.
- the final material is then a mesostructured photochromic film.
- the second major technique for the preparation of mesoporous or mesostructured photochromic films is called "direct synthesis.” This technique involves the dissolution of the photochrome in the precursor soil of the film in the presence of a pore-forming agent, and then the deposition and the polymerization of the soil. Generally, the blowing agent is not removed from the film structure.
- WO 02/41043 and the article "Fast response photochromic mesostructured", Wirnsberger, G .; Scott, BJ; Chmelka, BF; Stucky, GD Adv. Mater. 2000, 12, 1450-1454 describe the preparation by direct synthesis of silica matrix or transition metal-based mesostructured films by a poly (ethylene oxide) - poly (propylene oxide) triblock copolymer surfactant. ) - poly (ethylene oxide). The thickness of the films is several ⁇ m.
- the photochromic / Si molar ratio is typically between 1.5 ⁇ 10 3 and 3.5 ⁇ 10 3 .
- the patent WO 02/41043 also describes the covalent anchoring of the photochrome to the silica matrix or the triblock copolymer during the direct synthesis, by using a derivatised photochrome carrying a trialkoxysilane function, for example, capable of creating siloxane bridges with the precursors network or matrix already synthesized.
- anchoring to the matrix by a covalent bond is accompanied by a decrease in the efficiency of the photochromic because it is constrained.
- photochromes into a mesostructured silica powder incorporating a surfactant into its structure is described in the article "Photochromic mesostructured silica pigments dispersed in latex films", Andersson, N .; Alberius, P .; Ortegren, J .; Lingren, M .; Bergstrom, LJ Mater. Chem. 2005, 15, 3507-3513.
- the photochromic is added to a surfactant (PE10400) before the formation of the powder, so that finally it appears localized in the hydrophobic part of the micelles.
- the powder is then dispersed in a suspension of organic polymer (latex) and the whole is deposited in the form of 70 to 150 ⁇ m thick films.
- mesoporous silica matrix films are their low stability in the presence of a moisture-laden atmosphere. These films have a propensity to charge in water over time, which modifies their initial properties.
- photochromic films or layers having increased stability over time, in particular for applications in the field of optics, and more specifically ophthalmic optics.
- the object of the present invention is therefore to provide processes for the production of supports coated with photochromic films, in particular mesoporous films, having a hydrophobic matrix, which solve the above technical problems, and which can in particular be applied to any type of support. and in particular to transparent supports made of organic, thermally sensitive materials.
- the invention aims for processes which furthermore avoid any risk of deterioration of the photochromic properties of the photochromic compound during the preparation of the film, while ensuring a homogeneous distribution of this photochromic compound within the film.
- the invention also aims processes as above, wherein the photochromic compound has kinetic constants close to those observed in a solvent medium.
- the object of the invention is a support coated with a film as above, in particular an optical or ophthalmic lens.
- a first method of manufacturing a support coated with a mesoporous photochromic film comprising: a) preparing a precursor sol of a mesoporous film comprising:
- an inorganic precursor agent chosen from compounds of formula: M (X) 4 (I) in which the groups X, which are identical or different, are hydrolyzable groups preferably chosen from alkoxy, acyloxy and halogen groups, preferably alkoxy groups, and M represents a tetravalent metal or metalloid, preferably silicon; at least one organic solvent;
- the removal of the pore-forming agent is carried out at a temperature ⁇ 150 ° C., preferably ⁇ 130 ° C., better still ⁇ 120 ° C. and better still ⁇ 110 ° C. and
- the method comprises a step of introducing at least one hydrophobic precursor agent carrying at least one hydrophobic group into the precursor sol before the deposition step b) of the precursor sol film.
- the invention also relates to a second method of manufacturing a support coated with a photochromic film, comprising: a) the preparation of a precursor sol of a photochromic film comprising:
- an inorganic precursor agent chosen from compounds of formula:
- At least one porogenic agent at least one photochromic agent;
- the invention also relates to a third method for manufacturing a support coated with a photochromic film, comprising: a) the preparation of a precursor sol of a photochromic film comprising:
- an inorganic precursor agent chosen from compounds of formula:
- At least one photochromic agent at least one photochromic agent
- FIG. 1 is a representation of a part of the ternary diagram of the phases obtained in the TEOS / MTEOS / CTAB films, which makes it possible to determine the ordered or unordered structure of a film according to the invention prepared from the agent CTAB, the inorganic precursor agent TEOS and the hydrophobic precursor agent MTEOS. These compounds are explained in the description which follows.
- FIG. 2 is an example of a spectrum representing the variation as a function of time of the absorbance of a photochromic film subjected to interrupted UV irradiation as soon as the maximum absorbance of the film is reached, making it possible to access the kinetic constant of discoloration in the dark of the photochrome embedded in the mesoporous film.
- FIG. 3 is a schematic representation of the morphology of a mesoporous silica matrix film obtained after removal of the pore-forming agent. This is not a mesoporous film according to the invention, however a hydrophobic matrix mesoporous film according to the invention contains about the same amounts of micropores and mesopores as the silica film shown in FIG.
- hydrophobic groups is meant, in the context of the present invention, combinations of atoms that are not likely to associate with water molecules, especially by hydrogen bonding. These are usually nonpolar organic groups, free of charged atoms. Alkyl, phenyl, fluoroalkyl, (poly) fluoroalkoxy [(poly) alkyleneoxy] alkyl and hydrogen atom therefore fall into this category.
- all the steps of the three processes according to the invention are carried out at a temperature ⁇ 150 ° C., preferably ⁇ 130 ° C., better still ⁇ 120 ° C. and better still ⁇ 110 ° C.
- the precursor sols of mesoporous films are known and generally comprise at least one inorganic precursor agent of formula (I) or a hydrolyzate of this agent precursor, at least one organic solvent, a blowing agent and water, the medium in which the precursor agent of formula (I) is generally an acid medium, the acidic nature of the medium being obtained by addition, by for example, a mineral acid, typically HCl or an organic acid such as acetic acid, preferably HCl.
- This acid serves as a condensation catalyst by catalyzing the hydrolysis of X groups of the compound of formula
- this precursor sol comprises, in addition, at least one hydrophobic precursor agent carrying at least one hydrophobic group. It is usually introduced into the precursor soil as a solution in an organic solvent.
- the inorganic precursor agent of formula (I) and the hydrophobic precursor agent are the two precursor agents of the film matrix, the walls of which will surround the mesopores in the final mesoporous film.
- inorganic precursor is meant an organic or inorganic agent which, if polymerized alone, would lead to the formation of an inorganic matrix.
- a support coated with a mesoporous photochromic film can be obtained by dissolving at least one inorganic precursor agent of formula (I), at least one hydrophobic precursor agent and at least one porogenic agent in a mixture of water and organic solvent, generally in a hydro-alcoholic medium.
- heating may be employed to facilitate the dissolution of the various compounds.
- the soil is, if necessary, cooled and stirred under sufficient conditions (heating may be employed) to allow co-condensation of the precursors and possibly formation prior to the deposition of colloidal particles comprising the dispersed pore-forming agent. inside the growing network.
- the colloidal particles are formed during the deposition step.
- the pore-forming agent is removed, providing a mesoporous film with pores filled with air, optionally structured (which is only possible in the case where the pore-forming agent is of amphiphilic type), which is then impregnated with a solution containing at least one photochromic.
- a mesoporous photochromic film is obtained if the porogenic agent is not of the amphiphilic type, and a generally structured mesoporous photochromic film if the porogenic agent is of amphiphilic type.
- the inorganic precursor agent is chosen from compounds and mixtures of organometallic or organometalloid compounds of formula:
- the groups X are alkoxy groups, and in particular methoxy or ethoxy, and better ethoxy, which makes the inorganic precursor agent (I) a metal alkoxide or metalloid.
- M tetravalent metals represented by M
- metals such as Sn or transition metals such as Zr, Hf or Ti
- M preferably represents silicon and in this case the compound (I) is the precursor of a silica or silicate matrix of at least one metal.
- the preferred compounds (I) are tetraalkyl orthosilicates.
- tetraethoxysilane (or tetraethyl orthosilicate) Si (OC 2 Hs) 4 noted TEOS, tetramethoxysilane Si (OCH 3 ) 4 denoted as TMOS, or tetrapropoxysilane Si (OC 3 Hy) 4 denoted TPOS, are advantageously used, and preferably TEOS.
- the inorganic precursor agents of formula (I) present in the soil generally represent from 10 to 30% by weight relative to the total mass of the precursor sol.
- the hydrophobic precursor agent is preferably chosen from compounds and mixtures of compounds of formulas (II) or (III):
- M represents a tetravalent metal or metalloid, preferably Si, Sn, Zr, Hf or Ti, better silicon
- R 1 , R 3 and R 5 which may be identical or different, represent saturated or unsaturated hydrocarbon hydrophobic groups, preferably C 1 -C 8 and better still C 1 -C 4 groups , for example an alkyl group, such as methyl or ethyl, a vinyl group, an aryl group, for example phenyl, optionally substituted, in particular with one or more C 1 -C 4 alkyl groups, or represent the fluorinated or perfluorinated analogous groups of the abovementioned hydrocarbon groups, for example fluoroalkyl or perfluoroalkyl groups or (poly) fluoro groups; or perfluoroalkoxy [(poly) alkyleneoxy] alkyl.
- R 1 , R 3 and R 5 represent the methyl group.
- R 2 , R 4 and R 6 which are identical or different, represent hydrolysable groups, preferably chosen from alkoxy-OR groups, in particular C 1 -C 4 alkoxy, acyloxy-O-C (O) R, where R is an alkyl radical; preferably C 1 -C 6 , preferably methyl or ethyl, and halogens such as Cl, Br and I. They are preferably alkoxy groups, especially methoxy or ethoxy, and better ethoxy.
- R ' represents a divalent group, for example an optionally substituted linear or branched alkylene group, an optionally substituted cycloalkylene group, an optionally substituted arylene group or a combination of the above-mentioned groups, and category and / or different categories, including cycloalkylenealkylenes, biscycloalkylenes, biscycloalkylenealkylenes, arylenealkylenes, bisphenylenes and bisphenylenealkylenes.
- linear C 1 -C 10 alkylene groups for example the methylene -CH 2 - group, the ethylene group -CH 2 -CH 2 -, butylene, hexylene, especially 1,4- butylene and 1,6-hexylene and C 3 -C 10 branched alkylene radicals such as 1,4 (4-methylpentylene), 1,6- (2,2,4-trimethyl hexylene), 1, 5- (5-methylhexylene), 1-6- (6-methylheptylene), 1,5- (2,2,5-trimethylhexylene), 1,7- (3,7-dimethyloctenylene), 2, 2- (dimethylpropylene) and 1,6- (2,4,4-trimethyl hexylene).
- R 1 is preferably a methylene, ethylene or phenylene group.
- n 2 is an integer from 1 to 3
- n + n 2 4
- the preferred hydrophobic precursor agents are alkylalkoxysilanes, especially alkyltrialkoxysilanes, such as methyltriethoxysilane (MTEOS, CH 3 Si (OC 2 Hs) 3 ), vinylalkoxysilanes, especially vinyltrialkoxysilanes, such as vinyltriethoxysilane, fluoroalkyl alkoxysilanes, in particular fluoroalkyl trialkoxysilanes such as 3,3,3-trifluoropropyltrimethoxysilane of formula CF 3 CH 2 CH 2 Si (OCH 3 ) 3 and arylalkoxysilanes, especially aryltrialkoxysilanes. Dialkyldialkoxysilanes such as dimethyldiethoxysilane can also be used.
- the most preferred hydrophobic precursor agent is methyltriethoxysilane (MTEOS).
- the molar ratio of the hydrophobic precursor agent to the inorganic precursor agent of formula (I) ranges from 10/90 to 50/50, more preferably from 20/80 to 45/55, and is preferably 40 / 60, especially when using MTEOS as a hydrophobic precursor agent in precursor soil.
- the hydrophobic precursor agent carrying at least one hydrophobic group represents from 1 to 50% by weight relative to the total mass of the precursor sol.
- the organic solvents or the mixture of organic solvents suitable for the preparation of the precursor sol according to the invention are all solvents conventionally used, and more particularly the polar solvents, in particular the alkanols such as methanol, ethanol, isopropanol, propylene glycol, and the like. isobutanol, n-butanol and mixtures thereof.
- Other solvents, preferably water-soluble, may be employed, such as 1,4-dioxane, tetrahydrofuran or acetonitrile.
- the preferred organic solvent is ethanol.
- the organic solvent represents from 40 to 90% by weight relative to the total mass of the precursor sol.
- the water present in the precursor soil generally represents 10 to 20% by weight of the total mass of the precursor soil.
- the pore-forming agent of the precursor sol may be an amphiphilic or non-amphiphilic porogen. Generally, it is an organic compound. It can be used alone or mixed with other blowing agents.
- non-amphiphilic pore-forming agents that can be used in the present invention, mention may be made of:
- synthetic polymers such as polyethylene oxide, with a molar mass of between 50,000 and 300,000, polyethylene glycol, with a molar mass of between 50,000 and 300,000,
- gamma-cyclodextrin lactic acid
- other biological materials such as proteins or sugars such as D-glucose or maltose.
- the blowing agent is preferably an amphiphile of the surfactant type.
- An essential characteristic of such a compound is that it is capable of forming micelles in solution following the evaporation of the solvents which concentrate the solution, to lead to the formation of a mesostructured mineral matrix film. He plays the role of structuring agent.
- the surfactant compounds may be nonionic, cationic, anionic or amphoteric. These surfactants are for the most part commercially available.
- ionic surfactant compounds mention may be made of sodium dodecyl benzene sulphonate, ethoxylated fatty alcohol sulphates, cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), sodium dodecyl sulphate (SDS), azobiscyanopentanoic acid.
- nonionic surfactants mention may be made of ethoxylated fatty alcohols, ethoxylated acetylenic diols and compounds of the block copolymer type comprising both hydrophilic blocks and hydrophobic blocks, polyalkylenoxyalkyl ethers and surfactants incorporating a sorbitan group.
- PEO-PPO-PEO Polyoxyethylene-polyoxypropylene-polyoxyethylene
- poly (ethylenoxy) alkyl ethers of the general formula C n H 2n + 1 (OCH 2 CH 2 ) x OH are preferred, in particular those for which n> 12 and x > 8, such as surfactants marketed by ICI under the BRU denominations ®, such as BRIJ 56 ® (C 6 H 33 (OCH 2 CH 2) 10 OH), BRIJ 58 ® (C 6 H 33 (OCH 2 CH 2) 20 OH) and BRIJ 76 ® (polyoxyethylene (10) stearyl ether or C 18 H 37 (OCH 2 CH 2) 10 OH).
- BRIJ 56 ® C 6 H 33 (OCH 2 CH 2) 10 OH
- BRIJ 58 ® C 6 H 33 (OCH 2 CH 2) 20 OH
- BRIJ 76 ® polyoxyethylene (10) stearyl ether or C 18 H 37 (OCH 2 CH 2) 10 OH
- surfactants incorporating a sorbitan group can be used surfactants marketed by ICI under the name Tween ®, which are polyoxyethylene sorbitan esterified fatty acids, or surfactants marketed by Aldrich Chem. Co. under the name Span ®, which have a head sorbitan esterified fatty acids.
- the preferred blowing agents are CTAB and diblock or triblock copolymers, preferably triblock, of ethylene oxide and propylene oxide.
- the pore-forming agent represents from 2 to 10% of the total mass of the precursor sol.
- the ratio of the mass of porogenic agents to the sum of the mass of precursor agents of formula (I) and the mass of hydrophobic precursor agents carrying at least one hydrophobic group added to the precursor sol varies. from 0.01 to 5, preferably from 0.05 to 1.
- a particularly recommended method for preparing the precursor sol of a mesoporous film according to the first method of the invention is a two-step process for incorporating the precursor agents, comprising a first step of prehydrolysis and condensation. in the generally presence of an acid catalyst of the inorganic precursor agent of formula (I) as defined above (forming what will be called a "silica sol” in the case where the inorganic precursor agent of formula (I) is a precursor of silica), followed by a second mixing step with the hydrophobic precursor agent with optional concomitant introduction of the pore-forming agent.
- the advantage of such a hydrolysis in two steps is to be able to introduce high amounts of hydrophobic precursor agent and to reach a molar ratio of the hydrophobic precursor agent to the inorganic precursor agent of formula (I) as high as 50 / 50, preserving an orderly structure in the film.
- the hydrolysis is carried out in an acidic medium, adding water at a pH generally less than 4, more preferably less than 2, and most often from 1 to 2.
- the hydrolysis of the compound M (X) 4 is preferably carried out in the presence of a slight excess of water, typically a quantity of water of more than 1 to 1.5 times the molar amount of water. water required for stoichiometric hydrolysis of the hydrolyzable groups of the compound M (X) 4 .
- the reaction is then allowed to continue (aging of the soil).
- the sol is preferably maintained at a temperature of the order of 50 to 70 ° C., typically 60 ° C., for 30 minutes to 2 hours. Condensation can also be carried out at lower temperatures, but with longer condensation times.
- the precursor sol should be deposited and the precursor sol film formed rapidly after introduction of the hydrophobic precursor agent in the precursor sol, preferably in a time of 5 minutes or less, and better in a time of two minutes or less after introduction of the hydrophobic precursor agent. Proceeding in this very short time allows to minimize the condensation reaction of the hydrophobic precursor agent before the deposition and the formation of the film. In other words, it merely induces partial hydrolysis of the hydrophobic precursor agent without inducing a significant formation of condensed species from this agent.
- the deposition step b) of the precursor sol film on the main surface of the support can be done by any conventional method, for example dip coating, spray deposition or spin coating, preferably by centrifugation.
- the deposition step b) is carried out in an atmosphere having a relative humidity ratio (RH) ranging from 40 to 80%.
- the consolidation step c) of the structure of the deposited precursor sol film consists of possibly completing the removal of the solvent or mixture of organic solvents from the precursor sol film and / or the possible excess of water and continuing the condensation. , for example residual silanols present in the soil in the case of a silica-based matrix, generally by heating said film.
- step c) is carried out by heating at a temperature ⁇ 150 ° C., preferably ⁇ 130 ° C., better still ⁇ 120 ° C. and better still ⁇ 110 ° C.
- the removal of the blowing agent can be partial or total.
- step d) eliminates at least 90% by weight of the total mass of pore-forming agent present in the film resulting from the preceding step, better at least 95% by weight and better still at least 99% by weight. .
- This elimination is carried out by any appropriate method for working at low temperature, that is to say at a temperature ⁇ 150 0 C, preferably ⁇ 130 0 C, better ⁇ 120 0 C and better still ⁇ 110 0 C.
- solvent or fluid extraction in the supercritical state of ozone degradation, of plasma treatment, for example of oxygen or argon or corona discharge, or of photo-degradation by exposure to light radiation. This last technique is in particular described in application US 2004/0151651. Extraction with a supercritical fluid (typically supercritical CO 2 ) of a surfactant in a mesostructured material is practiced for example in patent JP 2000-226572.
- the removal of the pore-forming agent is by extraction. Several successive extractions can be performed, so as to reach the desired level of extraction.
- the extraction is carried out by means of an organic solvent or mixture of organic solvents by quenching the film formed and optionally consolidated in a solvent or a mixture of preferably organic solvents brought to a temperature ⁇ 150 ° C. preferably a refluxing solvent.
- a solvent or a mixture of preferably organic solvents brought to a temperature ⁇ 150 ° C. preferably a refluxing solvent.
- Any solvent having a boiling point ⁇ 150 ° C., preferably ⁇ 130 ° C., better still ⁇ 120 ° C. and better still ⁇ 110 ° C. may be suitable.
- a non-toxic solvent such as acetone or ethanol is preferably used.
- Acetone is particularly well suited to removal of surfactants of the CTAB or CTAC type by solubilization. Extraction with a solvent can also be effectively carried out at ambient temperature, with stirring, with the aid of ultrasound.
- the photochromic compounds which can be used in the present invention are in general organic compounds. These are generally hydrophobic compounds.
- a compound having photochromic properties is defined as a compound capable of undergoing reversible photo-irradiation chemical transformation from a first form to a second form having a different absorption spectrum.
- the photochromic agents that can be used in the context of the present invention are compounds which, when excited by light radiation, have at least one maximum absorption wavelength in the 400-700 nm range.
- the photochromic agents incorporated in the films of the process of the present invention may be, without limitation, oxazine derivatives, in particular spirooxazines, chromenes, photochromic compounds derived from chromene such as pyrans, in particular spiropyrans, fulgides and fulgimides, and organometallic derivatives of dithizonate, and mixtures thereof.
- the preferred oxazine compounds are spiro [indolino] benzoxazine, spiro [indolino] naphthoxazine and spiro [indolino] pyridobenzoxazine compounds.
- spiro [indolino] benzoxazine spiro [indolino] naphthoxazine
- spiro [indolino] pyridobenzoxazine compounds spiro [indolino] benzoxazine
- spiro [indolino] naphthoxazine and spiro [indolino] pyridobenzoxazine compounds.
- preferred oxazine compounds there may be mentioned compounds comprising the following basic unit
- R denotes a linear or branched alkyl group
- X denotes a carbon or nitrogen atom.
- the aromatic positions of this compound may be substituted. Specific examples of such compounds are the compounds of formulas (IV) to (VI) shown below
- chromenes and photochromic compounds of chromene are also well known and are described, inter alia, in EP 0246114, EP 0401958, EP 0562915, EP 0629656, EP 0676401, FR 2688782, FR 2718447, WO 90/07507, WO91 / 06861, WO 93/17071, WO 94/20869, US 3,567,605, US 5,066,818, US 5,395,567, US 5,451,344, US 5,645,767, US 5,656,206 and US 5,658,501.
- the chromene is represented by the following structure:
- the photochromic compounds comprising a preferred chromene unit may be represented by the formula:
- R 1 and R 2 represent radicals, identical or different, chosen from a hydrogen atom, an optionally substituted hydrocarbon radical and a substituted amino radical, or form in a ring combination
- R 3 and R 4 represent radicals, which may be identical or different, chosen from a hydrogen atom, an optionally substituted hydrocarbon radical and a substituted amino radical.
- a first preferred class is that of naphthopyrans, in particular those having two phenyl groups substituted or not on the carbon in position adjacent to the oxygen of the pyranic nucleus.
- Such photochromic compounds exhibit excellent resistance to degradation by radicals in an aqueous medium.
- An example of such a compound is the compound (VII) shown below:
- a second preferred class of chromene derivatives is spiropyrans.
- Preferred spiropyrans comprise the following basic unit:
- R denotes a linear or branched alkyl group.
- the aromatic positions of this compound may be substituted.
- An example of such a compound is the compound (VIII) shown below:
- photochromic fulgid and fulgimide compounds are known compounds and are described inter alia in US Patents 4,931, 220 and EP 0629656.
- organometallic compounds of dithizonate are known and described in US Pat. No. 3,361,706.
- Preferred photochromic compounds are chromene derivatives and oxazine derivatives such as benzoxazines and naphthoxazines, in particular spiro [indolino] benzoxazine, spiro [indolino] naphthoxazine and spiro [indolino] pyridobenzoxazine spirooxazine derivatives.
- the incorporation of the photochromic into the film can be carried out post-synthesis by impregnation using a mesoporous film already formed as a host (first method of the invention) or during the synthesis of the film itself (second and third methods of the invention, which will be described later).
- the mesoporous film resulting from step d) is impregnated with a solution of at least one photochromic agent dissolved in a solvent or a mixture of organic solvents.
- Said solvent must be able to establish favorable interactions with the mesoporous matrix in order to ensure a good diffusion of the photochromic agent in the matrix.
- the solvents that may be used, there may be mentioned in particular N, N-dimethylformamide (DMF), tetrahydrofuran (THF), ethanol, cyclohexane, N-methylpyrrolidone (NMP), and more generally any good solvent for photochromes (alkanes). , xylenes, toluene ).
- the photochromic agent solution may comprise, as adjuvant, a stabilizer for the photochromic compound.
- Impregnation of the film can be carried out, without limitation, by dipping the film-coated support in a solution of photochromic agent, or by centrifugally depositing a photochromic solution on the mesoporous film. At the end of this impregnation step, the support coated with a photochromic mesoporous film is recovered.
- the film is impregnated with the impregnation solution so as to obtain the desired photochromic effect in the final film.
- the mass of photochromic agent introduced into the film represents from 1 to 10% of the mass of the mesoporous film obtained after removal of the blowing agent and before the impregnation step.
- the mass of photochromic agent introduced into the film during the impregnation can be measured by carrying out its extraction, for example by dipping the photochromic film in a solvent.
- Any conventional photochromic agent alone or in admixture with other photochromic compounds, may be used in the process of the invention provided that they can be solubilized in a solvent or a mixture of solvents so that a solution for impregnate the mesoporous film of the invention.
- the first method of the invention further comprises a step of treating the film after step b) or if it exists, after step c), with at least one reactive compound hydrophobic carrier with at least one hydrophobic group, said hydrophobic reactive compound being different from said hydrophobic precursor agent.
- a step is intended to enhance the hydrophobicity of the film. It is declined in different forms in the literature.
- the application WO 99/09383 also describes the post-treatment of a mesoporous gel of TEOS with trimethylchlorosilane, after a solvent exchange has been carried out on the gel. After this post-treatment, the gel is dissolved again under the effect of an ultrasonic treatment, deposited on a substrate and calcined for one hour at 450 ° C.
- the additional step of post-treatment with said hydrophobic reactive compound is carried out at a temperature ⁇ 150 ° C., preferably ⁇ 130 ° C., better still ⁇ 120 ° C. and better still ⁇ 110 ° C.
- the treatment of the film with the hydrophobic reactive compound or with the mixture of hydrophobic reactive compounds is carried out according to the invention preferably by contact with the hydrophobic reactive compound or with the mixture of hydrophobic reactive compounds in the liquid state or with steam, preferably vapor, with said film.
- the hydrophobic reactive compound or with the mixture of hydrophobic reactive compounds in the liquid state or with steam, preferably vapor, with said film In the liquid phase, it is advantageous to dissolve the hydrophobic reactive compound in a solvent and to bring this solution to reflux by having previously immersed the film to be treated.
- the hydrophobic reactive compound is reactive with silanol groups. It is possible to use a large excess of hydrophobic reactive compound relative to the amount of silanol groups to be grafted to accelerate the reaction.
- this additional step called “postsynthetic grafting", is carried out during the removal step d) of the pore-forming agent.
- This variant is particularly suitable when this step d) is a solvent extraction step.
- the two treatments can be combined by using a solution of hydrophobic reactive agent carrying at least one hydrophobic group in a solvent for extracting the pore-forming agent.
- the additional post-synthetic grafting step is carried out after the removal step d) of the pore-forming agent but before the impregnation step e).
- the additional post-synthetic grafting step is carried out after the impregnation step e), that is to say on a film incorporating a photochromic agent.
- the additional post-synthetic grafting step is carried out before the step of removing the pore-forming agent.
- Hydrophobic reactive compounds carrying at least one hydrophobic group that is particularly suitable for the present invention are compounds of a tetravalent metal or metalloid, preferentially silicon, comprising a single function capable of reacting with the remaining hydroxyl groups in the film, particular an Si-Cl function,
- said hydrophobic reactive compound is chosen from compounds and mixtures of compounds of formula (IX):
- M represents a tetravalent metal or metalloid, for example Si, Sn, Zr, Hf or Ti, preferably silicon.
- the groups R 1 which may be identical or different, represent hydrocarbon hydrophobic groups that are saturated or unsaturated, preferably C 1 -C 8 and better still C 1 -C 4 , for example an alkyl group, such as methyl or ethyl, a vinyl group, an aryl group, for example phenyl, optionally substituted, in particular with one or more C 1 -C 4 alkyl groups, or represent the fluorinated or perfluorinated analogous groups of the abovementioned hydrocarbon groups, for example fluoroalkyl or perfluoroalkyl groups, or groups (poly) fluoro or perfluoro alkoxy [(poly) alkyleneoxy] alkyl.
- the group R 1 is a methyl group.
- the group R 2 represents a hydrolyzable group, preferably chosen from alkoxy-OR groups, in particular C 1 -C 4 alkoxy, acyloxy-O-C (O) R, where R is an alkyl radical, preferentially C 1 -C 6 alkyl; preferably methyl or ethyl, amino optionally substituted with one or two functional groups, for example an alkyl or silane group, and halogens such as Cl, Br and I. These are preferably alkoxy groups, especially methoxy or ethoxy, chloro or -NHSiMe 3 .
- a fluoroalkyl chlorosilane especially a tri (fluoroalkyl) chlorosilane or a fluoroalkyl dialkyl chlorosilane such as 3,3,3-trifluoropropyldimethyl chlorosilane of formula CF 3 -CH 2 -CH 2 -Si (CH 3 ) 2 Cl, an alkylalkoxysilane, especially a trialkylalcoxysilane as trimethylmethoxysilane (CH 3) 3 Si0CH 3, an alkoxysilane fluoroalkyl, especially a tri (fluoroalkyl) alkoxysilane or fluoroalkyl dialkyl alkoxysilane, an alkylchlorosilane, in particular a trialkyl chlorosilane such as trimethylchlorosilane, a kylsilazane trialkyl or hexaalkyldisil
- the hydrophobic reactive compound is necessarily different from the hydrophobic precursor agent employed in the precursor sol.
- the hydrophobic reactive compound comprises a kylsilyl trial group, preferentially a trimethysilyl group, and a silazane group, in particular a disilazane group.
- the particularly preferred hydrophobic reactive compound is hexamethyldisilazane (CH 3 ) 3 Si-NH-Si (CH 3 ) 3j denoted HMDS.
- the final photochromic film can be ordered or not.
- an amphiphilic porogen is preferably used as a structuring agent, so that the final photochromic film generally has an ordered structure.
- a structured film has better mechanical properties, and the means for controlling the reproducibility of its production process are easier.
- ordered or organized structure is meant a structure having a periodic organization in a thickness of at least 20 nm, and in a zone of dimension of at least 20 nm, preferably 300 nm in the plane of the deposited layer.
- the ordered structure may be in particular hexagonal type 3d, cubic or hexagonal 2d, at least locally.
- the hexagonal structure 3d consists of spherical micelles arranged in a network similar to a compact hexagonal stack. His space group is P6 3 / mmc.
- the cubic structure (space group Pm3n) is formed of ellipsoidal and spherical micelles.
- the hexagonal structure 2d (space group c2m) consists of cylindrical micelles.
- FIG. 1 appended to the present application represents a part of the ternary diagram of the phases obtained in the TEOS / MTEOS / CTAB films. It shows which ordered structures (phases) are obtained in the final gel from a soil comprising these three constituents according to the values of their molar ratios.
- MTEOS / TEOS reaches a limit value greater than 1, the films can no longer be structured.
- the mesoporous film according to the invention may have an organized structure of the hexagonal 3d, cubic or hexagonal 2d type, according to the proportion of CTAB used.
- the CTAB / TEOS molar ratios delimiting the phases move towards values that are higher as the MTEOS / TEOS molar ratio increases.
- the blowing agent is CTAB
- CTAB / TEOS an ordered hexagonal 3d structure for 0.210 ⁇ (CTAB / TEOS) ⁇ 0.280; an ordered structure of cubic type for 0.297 ⁇ (CTAB / TEOS) ⁇ 0.332;
- step a) the amounts of the two precursor agents and of the blowing agent are chosen in step a) so that the mesoporous films obtained according to the first method of the invention at the end of step d) have an ordered structure of hexagonal type 3d.
- the second and third methods of the invention which are so-called "direct synthesis” methods, will now be described. They differ from the first method in that the photochromic agent is incorporated in the precursor sol and not after the preparation of the mesoporous film.
- the second method generally involves the dissolution of at least one inorganic precursor agent, at least one hydrophobic precursor agent, at least one porogenic agent and at least one photochromic in a mixture of water and solvent. organic to form a precursor soil of a photochromic film.
- This precursor sol is polymerized and generally forms a mesostructured photochromic film in the case where the porogenic agent is of amphiphilic type, and a simply photochromic film in the case where it is not.
- incorporation of precursor agents in two steps is preferred.
- the third method of the invention differs from the second method in that the matrix is not rendered hydrophobic by incorporation into the precursor sol of at least one hydrophobic precursor agent, but by post-synthesis hydrophobation of the photochromic film by treatment of the latter. ci by at least one hydrophobic reactive compound bearing at least one hydrophobic group as described above. This means that no hydrophobic precursor agent is incorporated into the precursor soil.
- This post-synthesis hydrophobation step is carried out after the deposition step b) or if it exists after the consolidation step c). The realization of such a treatment on a film containing in its structure a pore-forming agent and / or a photochromic agent was not known.
- the film matrix is formed from only one type of precursor agent, the inorganic precursor agent.
- the incorporation of the photochromic agent into the precursor sol may be carried out by direct mixing, with stirring, of the photochromic agent or of a solution of the agent photochromic in an organic solvent or a mixture of organic solvents.
- This makes it possible to obtain a homogeneous solution of the photochromic agent in the precursor sol and consequently a homogeneous distribution in the final film.
- the solvents that may be used there may be mentioned in particular NN-dimethylformamide (DMF) and N-methylpyrrolidone (NMP).
- DMF NN-dimethylformamide
- NMP N-methylpyrrolidone
- the incorporation of the photochromic agent and the incorporation of the pore-forming agent in the precursor sol can be carried out simultaneously.
- An agent for stabilizing the photochromic compound can also be incorporated into the precursor sol.
- the photochromic agent in the precursor soil in the form of a dispersion of this photochromic in a solvent, provided that the precursor sol is finally homogeneous.
- the photochromic agent and the blowing agent can be one and the same compound, for example in the case where the photochromic agent also has surfactant properties.
- the precursor soil of the photochromic film has been prepared, it is recommended to rapidly deposit it on a main surface of the support. Indeed, the stability of a photochromic agent / sol mixture is very low, the photochromic agents used being sensitive to the acidic pH of the soil. The neutralization of the soil is not possible because it would cause the polymerization of the silica, and the synthesis of the films would not be reproducible.
- the support coated with a photochromic film, possibly mesostructured, is recovered.
- the photochromic compound is introduced into the precursor soil so as to obtain the desired photochromic effect in the final film.
- the photochromic agent introduced into the precursor sol represents from 0.05 to 10% by weight of the total mass of the precursor sol.
- any conventional photochromic agent alone or in admixture with other photochromic compounds, may be used in the second and third methods of the invention. Nevertheless, the photochromic agent must be sufficiently soluble in the precursor soil, which generally comprises a water / alkanol mixture. Thus, the maximum amount of molecules of photochromic compounds that can be incorporated into the film of the invention depends in this case on the solubility of these compounds in the precursor sol.
- both of these methods may include an additional step of selective removal of the blowing agent by any suitable technique, for example by selective extraction with a solvent, provided that removal takes place at a temperature of 150 ° C or less. C, preferably ⁇ 130 ° C., better ⁇ 120 ° C. and better still ⁇ 110 ° C., and does not affect the photochrome.
- a mesoporous photochromic film is obtained if the blowing agent is not of the amphiphilic type, and a generally structured mesoporous photochromic film if the blowing agent is of amphiphilic type.
- the additional step of selective removal of the blowing agent can be carried out before, during or after the optional (second process) or mandatory (third process) post-synthetic hydrophobation step.
- the photochromic is inserted within the hydrophobic part of the micelles, which results in its localization in the internal space of the mesopores or micelles in the final film.
- the photochromic films deposited according to the three processes of the invention generally have a maximum thickness of the order of 1 ⁇ m, and more generally a thickness ranging from 100 to 500 nm.
- a thickness ranging from 100 to 500 nm it is possible to successively deposit several films so as to obtain a multilayer film of desired thickness and therefore of sufficiently high absorbance.
- the thickness of this final multilayer film is determined by the importance of the desired photochromic effect and depends on the nature of the photochromic compound used.
- the support on which the films are deposited may consist of any solid material, transparent or non-transparent, such as mineral glass, a ceramic, a glass-ceramic, a metal or an organic glass, for example a thermoplastic or thermosetting plastic material.
- the support is a substrate of mineral glass or organic glass, preferably transparent.
- the support is a substrate made of a transparent plastic material.
- thermoplastic materials suitable for substrates mention may be made of
- polymers (meth) acrylic in particular poly (methyl methacrylate) (PMMA), thio (meth) acrylic (co) polymers, polyvinyl butyral (PVB), polycarbonates (PC), polyurethanes (PU) poly (thiourethanes), polyol allyl carbonates (co) polymers, ethylene / vinyl acetate thermoplastic copolymers, polyesters such as polyethylene terephthalate (PET) or poly (butylene terephthalate) (PBT), polyepisulfides, polyepoxides, polycarbonate / polyester copolymers, cycloolefin copolymers such as ethylene / norbornene or ethylene / cyclopentadiene copolymers and combinations thereof.
- PMMA poly (methyl methacrylate)
- PVB polyvinyl butyral
- PC polycarbonates
- PU polyurethanes
- PU polyurethanethanes
- (co) polymer is meant a copolymer or a polymer.
- (meth) acrylate is meant an acrylate or a methacrylate.
- alkyl (methacrylates) in particular (C 1 -C 4 ) alkyl (meth) acrylates, such as (meth) acrylate. of methyl and ethyl (meth) acrylate, polyethoxylated aromatic (meth) acrylates such as polyethoxylated bisphenol di (
- Examples of (co) polymers of polyol allyl carbonates include (co) polymers of ethylene glycol bis (allyl carbonate), diethylene glycol bis 2-methyl carbonate, diethylene glycol bis (allyl carbonate), ethylene glycol bis (2-chloro allyl carbonate), triethylene glycol bis (allyl carbonate), 1,3-propanediol bis (allyl carbonate), propylene glycol bis (2-ethyl allyl carbonate), 1,3-butenediol bis (allyl carbonate) ), 1,4-butenediol bis (2-bromo allyl carbonate), dipropylene glycol bis (allyl carbonate), trimethylene glycol bis (2-ethyl allyl carbonate), pentamethylene glycol bis (allyl carbonate), isopropylene bisphenol A bis (allyl carbonate).
- substrates obtained by (co) polymerizing the bis allyl carbonate of diethylene glycol, sold, e.g., under the trade name CR 39 ® from PPG Industries (ORMA lens ® ESSILOR).
- substrates obtained by polymerization of thio (meth) acrylic monomers, such as those described in French patent application FR 2734827 and polycarbonates.
- the substrates may be obtained by polymerization of mixtures of the above monomers, or may further comprise mixtures of these polymers and (co) polymers.
- the photochromic films of the invention may be formed on a main surface of a bare, i.e., uncoated substrate, or on a major surface of a substrate already coated with one or more functional coatings.
- the support of the invention is an ophthalmic lens substrate.
- ophthalmic optics it is well known to coat a main surface of a transparent organic material substrate, for example an ophthalmic lens, with one or more functional coatings to improve the optical and / or mechanical properties of the final lens.
- the main surface of the support may be provided beforehand with a primer coating improving the impact resistance (impact-resistant primer) and / or the adhesion of the subsequent layers in the final product, a coating resistant to the abrasion and / or scratches (hard coat), an anti-reflective coating, a polarized coating, another photochromic coating, a colored coating or a stack of two or more of these coatings.
- the impact-resistant primer coatings are preferably polyurethane latices or acrylic latices.
- the abrasion-resistant and / or scratch-resistant coatings are preferably hard coatings based on poly (meth) acrylates or silicone icons.
- a preferred anti-abrasion and / or anti-scratch coating composition is that disclosed in FR 2702486. It comprises an epoxy trialkoxysilane and dialkyl dialkoxysilane epoxy hydrolyzate, colloidal silica and a catalytic amount of a hardening catalyst. aluminum such as aluminum acetylacetonate, the remainder consisting essentially of solvents conventionally used for the formulation of such compositions.
- the hydrolyzate used is a hydrolyzate of ⁇ -glycidoxypropyltrimethoxysilane (GLYMO) and dimethyldiethoxysilane (DMDES).
- the mesoporous film according to the invention is itself preferably covered with a hydrophobic and / or oleophobic layer (top coat) whose thickness is generally less than 10 nm.
- a hydrophobic and / or oleophobic layer top coat
- These hydrophobic and / or oleophobic coatings are well known in the art and are generally obtained by conventional thermal evaporation techniques. They are generally made from fluorosilicones or fluorosilazanes, that is to say silicones or silazanes containing fluorine atoms.
- Fluorosilanes particularly suitable for forming hydrophobic and / or oleophobic coatings are those containing fluoropolyether groups described in US Pat. No. 6,277,485.
- R F is a monovalent or divalent polyfluoropolyether group
- R 1 is a divalent alkylene, arylene or a combination thereof, optionally containing one or more heteroatoms or functional groups and optionally substituted by halogens, and preferably containing 2 at 16 carbon atoms
- R 2 is a lower alkyl group (i.e., a C 1 -C 4 alkyl group)
- Y is a halogen atom, a lower alkoxy group (ie a group -C 4 alkoxy, preferably methoxy or ethoxy), or a lower acyloxy group (ie OC ( O) R 3 where R 3 is a C 1 -C 4 alkyl group; x is 0 or 1; and y is 1 (R F is monovalent) or 2 (R F is divalent).
- Suitable compounds generally have a number average molecular weight of at least 1000.
- Y is a lower alkoxy group and R F is
- Fluorosilane-containing compositions also recommended for the preparation of hydrophobic and / or oleophobic coatings are described in US Patent 6,183,872. They contain fluoropolymers containing organic groups bearing silicon-based groups represented by the following general formula and having a molecular mass of 5.10 2 to 1.10 5 :
- R F represents a perfluoroalkyl group
- Z is fluoro or trifluoromethyl
- a, b, c, d and e each independently represent 0 or an integer greater than or equal to 1, provided that the sum of a + b + c + d + e is not less than to 1 and that the order of the repetitive units appearing between the parentheses indexed under a, b, c, d and e is not limited to that represented
- Y is H or an alkyl group having 1 to 4 carbon atoms
- X represents a hydrogen, bromine or iodine atom
- R 1 represents a hydroxyl group or a hydrolyzable group
- R 2 represents a hydrogen atom or a monovalent hydrocarbon group
- I represents 0, 1 or 2
- m represents 1, 2 or 3
- n represents an integer at least equal to 1, preferably at least equal to 2.
- a preferred hydrophobic and / or oleophobic coating composition is marketed by Shin-Etsu Chemical under the name KP 801 M® .
- Another preferred hydrophobic and / or oleophobic coating composition is marketed by Shin-Etsu Chemical under the name KP 801 M® .
- Daikin Industries under the name OPTOOL DSX ® . It is a fluorinated resin comprising perfluoropropylene groups.
- the photochromic films according to the invention find application in very diverse fields: optical lenses, in particular ophthalmic lenses, in particular spectacle lenses, optical storage of information, guided optics (optical waveguides), diffraction gratings, Bragg mirrors, insulators for microelectronics, filtration membranes and stationary chromatography phases. This list is not exhaustive, of course.
- the support on which the photochromic film is formed according to the invention may also be a temporary support, on which said film is stored, waiting for transfer on a definitive support such as an ophthalmic lens substrate.
- Said temporary support may be rigid or flexible, preferably flexible. This is a removable medium, that is to say it is intended to be removed once made the transfer of the photochromic film on the final support.
- the temporary support may be employed having been previously coated with a layer of release agent to facilitate the transfer. This layer may optionally be eliminated at the end of the transfer step.
- the flexible temporary supports are generally thin elements of a few millimeters thick, preferably from 0.2 to 5 mm, better from 0.5 to 2 mm, made of a plastic material, preferably a thermoplastic material.
- thermoplastic (co) polymers that can be used for the manufacture of the temporary support are polysulfones, aliphatic poly (meth) acrylates, such as poly (meth) acrylate, polyethylene, polypropylene, polystyrene, SBM block copolymers (styrene-butadiene-methyl methacrylate), polyphenylene sulphide (PPS), arylene polyoxides, polyimides, polyesters, polycarbonates such as bisphenol A polycarbonate, polyvinyl chloride, polyamides such as nylons, copolymers thereof and mixtures thereof.
- the preferred thermoplastic material is polycarbonate.
- the main surface of the temporary support may comprise a stack of one or more functional coatings (already described) which will be transferred at the same time as the photochromic film of the invention to the final support.
- the coatings to be transferred were deposited on the temporary support in the reverse order with respect to the desired stacking order on the final support.
- the invention also relates to a method for transferring the photochromic film (or a stack of coatings comprising said photochromic film) of the temporary support to a definitive support.
- the methods of the invention then comprise the following additional step: z) the transfer of said photochromic film from the temporary support to a definitive support.
- the transfer of the coating or coatings carried by the temporary support can be carried out according to any appropriate technique known to those skilled in the art.
- Another object of the invention is an article comprising a support having a main surface coated with a photochromic film, said article being obtained or obtainable by one of the methods described above.
- Said photochromic film preferably has an ordered structure of hexagonal 3d type and said support is preferably made of an organic material.
- the article is preferably an ophthalmic lens.
- the support may be transparent and may comprise one or more functional coatings, the photochromic film may be deposited on any of them.
- the support may be a temporary support or a definitive support such as an optical substrate.
- the photochromic film is formed on an anti-abrasion and / or anti-scratch coating.
- the photochromic film is the penultimate layer in the stacking order, itself being coated with a hydrophobic and / or oleophobic layer.
- last layer of the stack refers to the layer furthest from the support.
- the TEOS of formula Si (OC 2 H 5 ) 4 was used as an inorganic precursor agent of formula (I), the MTEOS of formula CH 3 Si (OC 2 Hs) 3 was used as a precursor agent hydrophobic.
- Three surfactant-type pore-forming agents were tested: the CTAB of formula Ci 6 H 33 N (CH 3 ) 3 Br, the PE6800 denoted (EO) 73 - (PO) 28 - (EO) 73 , the PE10400 denoted (EO) 27 - (PO) 61 - (EO) 27 .
- the hydrophobic reactive compound used in some examples is hexamethyldisilazane (HMDS).
- the photochromic evaluated is the preferred photochromic of the invention, 5-methoxy-3,3-dimethyl-1-propylspiro [indoline-2,3 '- [3H] pyrido [3,2 - /] -
- the preparation of the precursor sol of a mesoporous film according to the first method of the invention is a two-step process of incorporation of the precursor agents.
- a silica sol comprising the inorganic precursor is prepared.
- the hydrophobic precursor agent is incorporated in this soil during a second step.
- the TEOS is hydrolysed then partially condensed by heating for 1 h at 60 ° C. in an ethanol medium.
- the silica sol produced consists of small polymeric clusters of partially condensed silica, with a large amount of silanol functions. These disappear in part if a hydrophobic precursor agent such as MTEOS is introduced into the soil. This synthesis was therefore designed so that the set ⁇ polymeric silica + MTEOS ⁇ remains sufficiently hydrophilic not to disturb the hydrophilic-hydrophobic balance of the system. Indeed, the polymerized MTEOS is hydrophobic, unlike the MTEOS hydrolyzed and uncondensed. Synthesis has also been designed to preserve the reactivity of silica clusters (specifically, their rate of gelation), which is usually altered by the presence of MTEOS.
- the resulting structure is shown in Table 1 below.
- the deposition takes place in a chamber whose hygrometry is controlled by a flow of nitrogen bubbling in a water tank.
- the atmosphere must be sufficiently moist (RH> 60%, with a sustained nitrogen flow), otherwise the organization of CTAB micelles into a periodic structure with large coherence domains does not occur properly.
- the film obtained using the CTAB as a blowing agent has a thickness of about 340 nm.
- CTAB The removal of CTAB can be followed by FTIR spectroscopy performed on the film after removing from the mixture and rinsing for a few minutes in acetone the substrate coated with the film. At the end of this step, a substrate coated with a mesoporous film is recovered.
- the films obtained are extremely porous (vacuum fraction of about 55%). They comprise both mesopores well calibrated, 4 nm in diameter (micelle imprint), and micropores, a few angstroms in diameter, located inside the walls of the matrix, and a priori non-monodisperse. With regard to the porous morphology of the various films, the mesopores generally represent 2/3 of the void volume and the micropores generally represent 1/3 of the void volume, which could be determined by subjecting the film to experiments of adsorption.
- Figure 3 shows schematically the morphology of a mesoporous silica matrix film obtained after removal of the pore-forming agent. In this figure appear two mesopores separated by microporous silica walls.
- a MTEOS / TEOS mesoporous matrix film contains about the same amounts of micropores and mesopores as the silica film shown in FIG.
- This treatment intended to increase the hydrophobicity of the film, is here carried out in the vapor phase.
- the substrate coated with the mesoporous film obtained in paragraph 4 is introduced into a Schlenk tube with 200 ⁇ l of HMDS.
- the assembly is placed under a static primary vacuum and then heated at 70 ° C. for 5 minutes.
- the good progress of grafting trimethylsilyl groups can be followed by FTIR spectroscopy performed on the film.
- the amount Grafted methyl groups are evaluated from the area of the Si-CH 3 band at 2965 cm -1 , relative to the thickness of the film, which makes it possible to prepare the mesoporous films of Examples 4 and 5, which differ by the nature of their matrix.
- the substrate coated with the mesoporous film obtained in paragraph 4 or 5 above (silica matrix or matrix MTEOS / TEOS, optionally post-treated with HMDS) is impregnated by centrifugal deposition of a photochromic solution of formula (IV) at 5 ⁇ 10 -3 mol / L in cyclohexane (3000 rpm for 2 minutes) A substrate coated with a mesoporous photochromic film is recovered.
- This treatment intended to increase the hydrophobicity of the film, is here carried out in the vapor phase.
- the substrate coated with the mesoporous photochromic film having undergone the treatments described in paragraphs 2 (hydrophobic matrix TEOS / MTEOS) then 4 and then 6 is introduced into a Schlenk tube with 200 ⁇ l of HMDS.
- the assembly is placed under a static primary vacuum and then heated at 70 ° C. for 5 minutes. This protocol makes it possible to prepare the mesoporous photochromic film of example 6. It was verified that the hexagonal 3d type ordered structure was preserved after treatment with HDMS.
- the photochromic film is irradiated in the UV, which induces a coloration of this film.
- FIG. 2 is an example of a spectrum obtained during this type of study, and carried out less than 24 hours after the preparation of the photochromic film.
- the use of a bi-exponential model is sometimes necessary, which indicates that the photochromic is localized in several different environments, for example, in the mesopores and in the walls separating them.
- Example 2 the photochrome of formula (IV) was incorporated in various mesoporous films by impregnation, as described in paragraph 6 above.
- the non-mesoporous film of Example 7 was prepared by adding photochromics to the soil prior to deposition.
- Example 1 the photochromic solution is deposited on a dense surface (glass slide).
- Example 2 mesoporous film with silica matrix.
- Example 3 mesoporous matrix film of MTEOS / TEOS 40/60.
- Example 4 mesoporous silica matrix film rendered hydrophobic only by post-synthetic HMDS treatment.
- Example 6 mesoporous matrix film of MTEOS / TEOS 40/60 post-treated with HMDS after impregnation.
- Example 7 sol-gel film dense (non-mesoporous) and soft (poorly crosslinked, Tg ⁇ 0 0 C) in which the photochromic is dispersed, as described in FR 2795085 or J. Mater. Chem. 1997, 7, 61-65.
- ⁇ max is the position of the absorbance maximum of the system in its colored form (in the visible).
- a m3x is the corresponding absorbance.
- Table 2 shows that the kinetic constants of discoloration in the dark are very dependent on the nature of the photochromic host.
- the photochromic molecules are aggregated and are no longer active, which results in a low absorbance (0.02). This is the case of Example 1 (no matrix) and Example 4. Without being limited by a particular theory, the inventors believe that this is due to steric reasons, which is explained below.
- a high value of ⁇ max (630 or 634 nm) is another index of aggregation. This value was obtained when the photochrome is deposited on dense surfaces of various natures (hydrophilic or hydrophobic).
- the two parameters ⁇ max and A m3x make it possible to identify the cases in which the photochrome fails to diffuse correctly within a porous structure.
- a comparison of the results of Examples 2 and 3 reveals the superiority of a hydrophobic matrix (MTEOS / TEOS) on a silica matrix in terms of ensuring proper operation of the photochromic, its good diffusion into the mesopores during the course of time. impregnation stage and its good dispersion within the matrix.
- the best value of A max in Example 3 indicates, a priori, a greater amount of photochromic agent incorporated in the film.
- only the MTEOS / TEOS matrix makes it possible to obtain fast staining and fading kinetics.
- the post-treatment of a mesoporous film by the HMDS before its photochromic impregnation improves the kinetics of staining and discoloration, whether the initial matrix is hydrophobic or not, but limits the diffusion of photochromics in the mesopores. This is perfectly understandable, since a non-post-graft mesoporous film is much more porous than the same post-graft film. A satisfactory value of A max, however, is obtained for the film of Example 5 according to the invention, having a post-grafted MTEOS / TEOS matrix.
- the post-treatment of the silica matrix film by the HMDS which makes it possible to obtain a hydrophobic matrix, causes the aggregation of the photochrome on the surface of the film, and therefore a low absorbance results.
- the post-treatment of a mesoporous film with silica matrix by the HMDS makes disappear 3/4 of the micropores present within the walls. The walls are densified, which limits the diffusion of the photochrome and prevents its access within the film.
- the inventors believe that aggregation phenomenon is not detected when the photochromic is incorporated in a MTEOS / TEOS hydrophobic matrix film post-HMDS processed because the matrix films hydrophobic MTEOS / TEOS contain fewer SiOH silanols groups that can be grafted with HMDS. The reduction in porosity induced by this grafting is therefore lower.
- the staining and fading kinetics are comparable, whether the HMDS post-treatment is carried out before or after the photochromic impregnation of the film, in the case of a MTEOS / TEOS hydrophobic matrix film. .
- a stock solution of blowing agent containing 48.7 g of CTAB per liter of ethanol is prepared. Its dissolution can be facilitated by the use of ultrasound for a few seconds. 6.7 ml of this stock solution are taken and added to 21.7 mg of photochrome of formula (IV), and 0.75 ml of pure MTEOS is then added to this mixture.
- the films obtained have an ordered structure of the type hexagonal 3d. This protocol makes it possible to prepare the photochromic film of Example 11.
- HCI-H 2 O 1: 3.8: 5
- respective volumes 5 mL, 2.5 mL and 3 mL are cooled to 20 ° C., added respectively to 112 ⁇ L, 56 ⁇ L and 67 ⁇ L of acidified water.
- HCI pH 1.25
- the films obtained are all structured (verified by X-ray diffraction).
- a CTAB mesostructured silica matrix film identical to that of Example 8 above, is treated with HMDS in the vapor phase at 70 ° C under static primary vacuum as described in paragraph A) 5. above, but overnight rather than 5 minutes.
- This difference in treatment time is due to the fact that the treated film incorporates this time into its structure a photochromic and a pore-forming agent. This protocol makes it possible to prepare the photochromic film of Example 12.
- Example 8 the photochrome of formula (IV) was incorporated into various films by direct synthesis, as described in paragraphs 1 to 3 above.
- the non-mesoporous film of Example 7 was prepared by adding photochromics to the soil prior to deposition.
- Example 7 sol-gel film dense (non-mesoporous) and soft (poorly crosslinked, Tg ⁇ 0 0 C) in which the photochromic is dispersed, as described in FR 2795085 or J. Mater. Chem.
- Example 8 silica matrix film, mesostructured by CTAB.
- Example 9 silica matrix film, mesostructured with PE6800.
- Example 10 (comparative): silica matrix film, mesostructured with PE10400.
- Example 11 (second method of the invention): MTEOS / TEOS 40/60 matrix film, mesostructured by CTAB.
- Example 12 silica matrix film post-treated with
- HMDS mesostructured by CTAB.
- the photochromic film hydrophobic matrix according to the invention has the advantage of being insensitive to a humid atmosphere, which results in increased stability of its properties over time.
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Abstract
Description
Claims
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FR0650380A FR2896886B1 (fr) | 2006-02-02 | 2006-02-02 | Procedes de fabrication d'un article revetu d'un film photochrome et leur application en optique ophtalmique |
PCT/FR2007/050718 WO2007088312A1 (fr) | 2006-02-02 | 2007-01-31 | Procedes de fabrication d'un article revetu d'un film photochrome et leur application en optique ophtalmique |
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EP1979281A1 true EP1979281A1 (fr) | 2008-10-15 |
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EP07731546A Withdrawn EP1979281A1 (fr) | 2006-02-02 | 2007-01-31 | Procedes de fabrication d'un article revetu d'un film photochrome et leur application en optique ophtalmique |
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US (1) | US20130108858A1 (fr) |
EP (1) | EP1979281A1 (fr) |
JP (1) | JP2009525497A (fr) |
FR (1) | FR2896886B1 (fr) |
WO (1) | WO2007088312A1 (fr) |
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US9896549B2 (en) * | 2010-04-13 | 2018-02-20 | Aaron Kessman | Hydrophobic and oleophobic coatings |
FR2965820B1 (fr) | 2010-10-12 | 2012-11-16 | Essilor Int | Article comprenant une couche mesoporeuse protegee par un revetement faisant barriere au sebum et procede de fabrication |
US20120237676A1 (en) * | 2011-03-14 | 2012-09-20 | Intermolecular, Inc. | Sol-gel based formulations and methods for preparation of hydrophobic ultra low refractive index anti-reflective coatings on glass |
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EP2752388A1 (fr) * | 2012-12-13 | 2014-07-09 | Guardian Industries Corp. | Procédé de fabrication d'article revêtu comprenant un revêtement antiréfléchissant et produits le contenant |
EP2752387B1 (fr) * | 2012-12-13 | 2018-06-27 | Guardian Glass, LLC | Procédé de fabrication d'article revêtu comprenant un revêtement antiréfléchissant ayant des couches de revêtement double incluant des matériaux mésoporeux et produits les contenant |
CN103456243B (zh) * | 2013-08-23 | 2016-05-11 | 京东方科技集团股份有限公司 | 一种幕墙 |
EP2887129B1 (fr) | 2013-12-23 | 2020-04-22 | Essilor International | Article optique transparent présentant un aspect incolore |
WO2015097169A1 (fr) | 2013-12-23 | 2015-07-02 | Essilor International (Compagnie Generale D'optique) | Afficheur facial avec fonction de filtrage |
US10114234B2 (en) | 2013-12-23 | 2018-10-30 | Essilor International (Compagnie Generale D'optique | Transparent optical article having a reduced yellowness appearance |
US20160041307A1 (en) * | 2014-08-08 | 2016-02-11 | Ppg Industries Ohio, Inc. | Method of forming an anti-glare coating on a substrate |
US9707592B2 (en) * | 2014-08-08 | 2017-07-18 | Ppg Industries Ohio, Inc. | Method of forming an anti-glare coating on a substrate |
EP3195027A2 (fr) | 2014-09-03 | 2017-07-26 | Essilor International (Compagnie Générale D'Optique) | Dispositif optique |
KR101673720B1 (ko) * | 2014-12-30 | 2016-11-23 | 현대자동차주식회사 | 김서림 방지용 다공성 실리카 박막의 제조방법 |
EP3086164A1 (fr) | 2015-04-23 | 2016-10-26 | ESSILOR INTERNATIONAL (Compagnie Générale d'Optique) | Article optique teinté |
JP6579837B2 (ja) * | 2015-07-15 | 2019-09-25 | 株式会社トクヤマ | フォトクロミック組成物 |
KR102499750B1 (ko) | 2015-11-06 | 2023-02-15 | 에씰로 앙터나시오날 | 청색광으로부터 보호하는 광학 물품 |
CN108351536B (zh) | 2015-11-06 | 2020-09-08 | 依视路国际公司 | 保护免受蓝光以及紫外光的光学制品 |
LU93013B1 (en) * | 2016-04-04 | 2017-11-08 | Cppe Carbon Process & Plant Eng S A En Abrege Cppe S A | Process for the removal of heavy metals from fluids |
LU93014B1 (en) | 2016-04-04 | 2017-10-05 | Ajo Ind S A R L | Catalyst mixture for the treatment of waste gas |
LU93012B1 (en) | 2016-04-04 | 2017-11-08 | Cppe Carbon Process & Plant Eng S A En Abrege Cppe S A | Sulfur dioxide removal from waste gas |
EP3232254B1 (fr) | 2016-04-11 | 2024-01-03 | Essilor International | Système optique pour le traitement de troubles chronobiologiques et/ou de la myopie |
EP3301488A1 (fr) | 2016-09-29 | 2018-04-04 | Essilor International | Lentille optique comprenant un revêtement antireflet à efficacité multiangulaire |
JP6542982B2 (ja) * | 2016-10-11 | 2019-07-10 | 三井化学株式会社 | 光学材料用重合性組成物およびその用途 |
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PT3327091T (pt) | 2016-11-23 | 2023-04-19 | Essilor Int | Composição epóxi funcional que protege corantes da fotodegradação e revestimentos curados preparados a partir da mesma |
EP3327488B1 (fr) | 2016-11-23 | 2021-01-06 | Essilor International | Article d'optique comportant un colorant résistant à la photodégradation |
US11054558B2 (en) | 2016-12-02 | 2021-07-06 | 3M Innovative Properties Company | Photochromic articles containing a porous material with a photochromic dye and fluid, methods of making and using |
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- 2007-01-31 WO PCT/FR2007/050718 patent/WO2007088312A1/fr active Application Filing
- 2007-01-31 US US12/278,130 patent/US20130108858A1/en not_active Abandoned
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WO2007088312A1 (fr) | 2007-08-09 |
JP2009525497A (ja) | 2009-07-09 |
FR2896886A1 (fr) | 2007-08-03 |
US20130108858A1 (en) | 2013-05-02 |
FR2896886B1 (fr) | 2008-07-11 |
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