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  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
  • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
  • C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
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  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
  • C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
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  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
  • C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
  • C09C1/0087—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide only containing titanium dioxide and silica or silicate
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  • C09C1/0096—Compounds of antimony
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  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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  • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
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  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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• • G—PHYSICS
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  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31935—Ester, halide or nitrile of addition polymer
• • 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
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

• the invention relates to a hybrid organic-inorganic composite material comprising particles of an inorganic compound functionalised on the surface by an organic compound, and an organic polymer.
• This hybrid material may in particular be in the form of an optical thin layer or an absorbent colored layer.
• Optical thin film in the sense of the invention generally means a layer which allows the realization of transparent coatings preferably in a range of wavelengths between the ultraviolet and the near infrared, this range of wavelengths includes the visible spectrum.
• transparent coating means a material, coating, which can be traversed by light rays of wavelengths lying in the spectral range, the spectral range of interest which is for example the range defined above.
• thin film are also used, thin films of "optical quality" which signify that these transparent films do not exhibit diffusion and / or absorption in the spectral range of interest.
• the invention further relates to an optical material comprising said layer or hybrid organic-inorganic material.
• the invention finally relates to a process for the preparation of this material and of these thin layers.
• hybrid material or inorganic-organic composite is meant a material comprising at least one component of organic nature such as an organic polymer and at least one inorganic component such as mineral particles of metals or metalloids, or metal compounds or metalloids, such as oxides of metals or metalloids.
• the document [1] describes a composite material with a high refractive index, its manufacturing method, as well as optically active materials, especially anti-reflective materials and reflecting materials made from this composite material.
• a suspension of colloidal metal oxides dispersed in an aliphatic alcohol is prepared; we mixing said colloidal suspension with a polyvinyl polymer soluble in a solvent containing an alcohol; depositing the mixture or soil obtained on a support to form a uniform layer; and this layer is crosslinked by ultraviolet treatment.
• the colloidal particles are not functionalized on the surface by reaction with an organic compound but simply embedded in a polyvinyl polymer.
• a toluene suspension is prepared for surface-modified silica nanoparticles with isooctylsilane, or a colloidal silica suspension surface-modified with a silane in ultrapure water.
• Hybrid solutions comprising inorganic nanoparticles in an organic or inorganic polymer solution, especially in a solution of organic polymer in an organic solvent, aprotic, apolar are not described in this document which does not mention the preparation of true inorganic-organic hybrid materials comprising an organic polymer.
• Documents [3] and [4] indicate the possibility of dispersing copper or silver particles in various organic polymers such as polyvinyl methyl ketone, PVC, polyvinylidene fluoride or nylon-11.
• organic polymers such as polyvinyl methyl ketone, PVC, polyvinylidene fluoride or nylon-11.
• the solubilization of these polymers in organic solvents of the tetrahydrofuran and acrylonitrile type makes it possible to ensure good stability of the metal particles.
• it does not implement colloidal nanoparticles of oxides or functionalized metal oxyhydroxides, but nonfunctionalized metal particles.
• Document [5] relates to nanocomposites containing an organic matrix, in particular a polymer and nanoparticles, each of these nanoparticles comprising at least one metal sulphide nanocrystal whose surface is modified with a carboxylic acid with at least one aryl group.
• the nanoparticles are prepared by forming a solution of a non-alkali metal salt and the carboxylic acid in apolar, aprotic solvent and adding a sulfide to this solution and precipitating the nanoparticles formed by adding a third solvent.
• the nanocomposites are prepared by mixing the nanoparticles with the organic matrix to dissolve the nanoparticles. If the organic matrix comprises polymerizable, heat-curable or irradiating monomers, an initiator is added to the mixture and the polymerization, radiation curing or heating is carried out.
• nanocomposites can be used in optical applications.
• the nanoparticles are not prepared by a sol-gel process in a protic, polar medium.
• teachings of this document apply specifically to sulphides such as ZnS, transparent in the infrared, and can in no way be easily transposed to particles of other materials, such as oxides such as ZnO transparencies in the visible.
• Document [6] describes coating solutions comprising surface-modified nanoparticles, a first liquid and a second liquid, the nanoparticles being more compatible with the first liquid than with the second liquid.
• the first liquid is removed for example by evaporation and the other liquid generally forms a film.
• the first liquid may be chosen in particular from aliphatic, alicyclic and aromatic organic solvents such as toluene, alcohols, ketones, aldehydes, amines, amides, esters, glycols, ethers and the like.
• the second liquid may be a curable liquid, curable by heat, irradiation, or moisture.
• the nanoparticles may be mineral nanoparticles, for example nanoparticles of metal oxides such as silica, zirconia, titanium oxide, tin oxide and the like.
• the nanoparticles may in particular be in the form of colloidal dispersions, for example zirconium oxide or titanium oxide.
• the colloidal particles are prepared by a hydrolysis condensation process such as a sol-gel process and if the dispersions are dispersions in a polar or protic solvent.
• the groups modifying the surface of the nanoparticles are chosen to ensure the compatibility of the nanoparticles with at least one of the liquids, thus when the liquid is hydrophobic, for example toluene, ketones and acrylates the surface groups will be chosen to ensure compatibility with this hydrophobic liquid.
• silanes organic acids and bases and alcohols.
• coating solutions are prepared with surface-modified silica by trialkoxysilane coupling agents to render it hydrophobic, poly (methyl methacrylate), toluene, and 1-methoxy-2 acetate. propanol and these solutions are deposited on glass slides.
• silica C is in the form of a clear blue solution of low viscosity, the solvent of which is not specified. .
• the other silicas A and B are dried beforehand.
• the silicas A, B, 1-methoxy-2-propanol acetate and toluene are added to a solution of PMMA in toluene to give coating solutions ([0099] - page 7).
• Solution C is mixed with HDDA (1,6-hexanediol diacrylate) to give a viscous gel which is added to a mixture of HDDA and THF. There is therefore no exchange of solvents but simply addition, mixture of solvents. To the resulting mixture is added DAROCUR ® which is a curing agent (Example 14, paragraphs [0105] and [0106] page 8).
• the nanoparticles are not added to a polymer already prepared, constituted, but soluble monomers which then polymerize; and in the case where the nanoparticles are in suspension (C) a compound is added thereto
• the process of this document can not be performed with all polymers.
• the process of this document excludes any polymers that can not be prepared by in situ polymerization from soluble monomers; this is particularly the case of polytetrafluoroethylene
• Document [7] relates to a colloidal system of nanoparticles of mineral oxides in a dispersion medium such as water, alcohol, tetrahydrofuran, halogenated hydrocarbons, dilute sodium hydroxide solution, dilute acids, hydrocarbons and aromatic hydrocarbons.
• a dispersion medium such as water, alcohol, tetrahydrofuran, halogenated hydrocarbons, dilute sodium hydroxide solution, dilute acids, hydrocarbons and aromatic hydrocarbons.
• the nanoparticles are in particular nanoparticles of titanium oxide, zirconium oxide, aluminum oxide, iron oxide, barium titanate or "ITO” ("Indium Tin Oxide” in English).
• these particles are modified, functionalized on the surface by mineral acids, beta-diketones; isocyanates; organic acids; acid chlorides of esters, silanes of polycarboxylic acids.
• mineral acids beta-diketones
• isocyanates organic acids
• acid chlorides of esters silanes of polycarboxylic acids.
• colloidal systems make it possible to improve certain components in ceramics or plastics. They can be used as a charge for thermal or sound insulation, in nanofiltration diaphragms, in gas detectors, or in hollow ceramic fibers. This document neither describes nor suggests the addition of organic polymers to these colloidal dispersions, nor their deposition in the form of thin films, in particular for the production of hybrid thin films of optical quality.
• the document [8] relates to mixtures of immiscible polymers whose morphology and microstructure are altered by surface-modified nanoparticles in particular by silanes, organic acids, organic bases and alcohols.
• These nanoparticles may be inorganic particles such as silica particles, zirconia, titanium oxide, silica, cerium oxide, alumina, iron oxide, vanadium oxide, antimony oxide, tin oxide.
• the nanoparticles facilitate the uniform distribution of the dispersed phase of the polymer mixture in the continuous phase of this mixture.
• Various methods can be used to combine the surface-modified nanoparticles and the continuous phase. For example, a colloidal dispersion of surface-modified nanoparticles can be combined with the continuous phase, then the solvent is removed and the continuous phase in which the surface-modified nanoparticles are dispersed is obtained.
• colloidal dispersion is an aqueous dispersion
• a cosolvent may be added to facilitate removal of the water. After the addition of the continuous phase, the water and cosolvent are removed.
• a mixture of an acrylic adhesive forming the continuous phase and a KRATON polymer forming the dispersed phase is prepared by extrusion with the addition of porous silica particles surface-modified with a silane.
• Document [9] relates to the dispersion of nanoparticles of tungsten oxide in polyacrylonitrile itself dissolved in dimethylformamide. This document does not envisage the functionalization of the surface of the nanoparticles to improve the dispersion of the nanoparticles in an organic medium.
• the solvent envisaged is not conducive to the production of thin films by liquid, because it has a saturation vapor pressure too low. The production of thin films by this method produces films with surface inhomogeneities.
• US-A-5, 134, 021 [10] discloses an anti-fog film which comprises at least two layers of a film cured on a substrate, said cured film comprising as main components: (A) alcohol polyvinyl (PVA) and (B) at least one compound selected from colloidal silica, an organosilicon compound, and the product of the hydrolysis of said compound organosilicon.
• the organosilicon compound acts as a binder and is not intended to render the silica compatible with a solvent but rather to impart anti-fogging properties to the film.
• an aqueous solution of PVA is prepared, and then a hydrolyzed silane and a silica sol in methanol are added to this solution. Then, dioxane and a fluorinated surfactant and aluminum acetylacetonate (catalyst) are added to this mixture to obtain a coating composition.
• FR-A-2 681 534 [11] describes concentrated colloidal solutions of unaggregated monocrystalline particles of metal oxides in a non-aqueous solvent.
• These particles are prepared by complexation in a non-aqueous solvent medium of a compound such as a metal alkoxide with a ligand, and then hydrolysis and condensation of the complex formed with the aid of an aqueous solution of a strong acid. At the end of this step, a sol of amorphous particles of metal oxides whose surface is protected by the complexing agents, ligands, is obtained.
• an anti-fog film comprising a cured film derived from (A) a polyvinyl alcohol; (B) finely divided silica; and (C) a compound selected from organosilicon compounds and hydrolysates thereof.
• US-A-4, 170, 690 discloses a coating composition, particularly for imparting abrasion resistance to thermoplastic substrates, which comprises a colloidal silica, and a mixture of a dialkyldialkoxysilane and a an alkyltrialkoxysilane.
• This coating composition is prepared by adding a mixture of a dialkyldialkoxysilane and an alkyltrialkoxysilane to a colloidal silica hydrosol and adjusting the pH.
• a coating composition comprising water of the colloidal silica, acetic acid, methyl trimethoxysilane, and dimethyl dimethoxysilane which is diluted with isopropanol to 20% solids.
• the coating composition does not contain polymer and no solvent exchange is carried out.
• the solvent is always a substantially aqueous, polar solvent.
• Document FR-A-2 882 746 [14] describes a process for preparing a sol-gel solution and the use of this solution to form a coating for protecting a metal-surface substrate.
• the method comprises the following steps: a) preparing a sol-gel solution by contacting one or more molecular precursors of metal and / or metalloid with a medium comprising an organic solvent; b) adding to the solution obtained in a) at least one mercaptoorganosilane compound; c) hydrolyzing the solution obtained in b); d) adding to the solution obtained in c) one or more complexing agents.
• a layer of the sol-gel solution prepared as described above is deposited on the substrate and the deposited layer is cross-densified.
• the method of this document does not include a step of grafting an organic compound onto the particle surface or solvent exchange stage.
• FR-A-2 680 583 [15] describes a material with antireflection, hydrophobic and abrasion resistance properties.
• This material comprises, in particular, an antireflection sol-gel layer formed of silica colloids in a siloxane binder.
• This layer is prepared from a sol-gel solution, itself prepared by hydrolyzing a precursor, for example TEOS, in a basic medium. At the same time, the precursor is also hydrolyzed in an acidic medium in order to produce the soluble siloxane binder.
• the silica is not functionalized on the surface by reaction with an organic compound.
• the silica is simply coated without a chemical reaction between the siloxane and the surface of the silica.
• the object of the present invention is to provide a hybrid material, organic-inorganic composite that meets this need, among others.
• the object of the present invention is still to provide a hybrid material, organic-inorganic composite which does not have the disadvantages, defects, limitations and disadvantages of the materials of the prior art and which solves the problems of hybrid materials, composites of the prior art.
• an organic-inorganic (hybrid) composite material comprising:
• the hydrolysis-condensation process by which the colloidal particles are prepared is generally chosen from hydrothermal processes and sol-gel processes, the latter being preferred.
• the hydrothermal processes use a reaction medium under pressure and at a temperature in which the hydrolysis-condensation and crystallization reactions are kinetically favored.
• sol-gel processes involve synthesis from inorganic precursors such as salts, or organometallic precursors such as alkoxides, metal oxides under "soft" conditions of temperature and pressure, ie generally under pressure. atmospheric and at a temperature below 100 ° C.
• the colloidal particles may have any shape, for example spherical or quasi-spherical particles, spheroidal, polyhedral particles, anisotropic particles having in particular the form of platelets or grains of rice.
• the colloidal particles generally have an average size, defined for example by their characteristic size, which is the diameter in the spherical or spheroidal particles, from 1 to 100 nm, preferably from 2 to 50 nm.
• the oxides of metal or metalloids may be chosen from transparent oxides, especially in the visible, or colored. These oxides may be chosen in particular from scandium, yttrium, lanthanum, titanium, zirconium, hafnium, thorium, niobium, strontium, tantalum, cerium, antimony, tin, nickel, magnesium, manganese, iron, cobalt, germanium, and silicon oxides. ; mixed oxides thereof; and mixtures of these oxides and mixed oxides.
• the oxyhydroxides of metal or metalloids may be chosen from transparent oxyhydroxides, especially in the visible, or colored.
• oxyhydroxides may be chosen in particular from the oxyhydroxides of scandium, yttrium, lanthanum, titanium, zirconium, hafnium, thorium, niobium, strontium, tantalum, cerium, antimony, tin, nickel, magnesium, manganese, iron, cobalt, germanium, and silicon. ; mixed oxyhydroxides thereof; and mixtures of these oxyhydroxides and mixed oxyhydroxides.
• the protic or polar solvent may be selected from water; saturated or unsaturated aliphatic alcohols of formula ROH, where R represents an alkyl group of 1 to 30 carbon atoms or a phenyl group; diols of formula HOR 'OH wherein R' represents an alkyl group of 1 to 30 carbon atoms or a phenyl group; and mixtures thereof.
• ROH saturated or unsaturated aliphatic alcohols of formula ROH, where R represents an alkyl group of 1 to 30 carbon atoms or a phenyl group
• diols of formula HOR 'OH wherein R' represents an alkyl group of 1 to 30 carbon atoms or a phenyl group
• the protic or polar solvent is methanol.
• the organic compound whose reaction with the surface of the particles allows the functionalization thereof in other words the organic compound which is grafted onto the surface of the particles is preferably an organosilane or a complexing molecular compound.
• the organosilane can meet the following formula (I):
• R 1 is an alkyl group of 1 to 10 carbon atoms
• X is a hydrolyzable group such as a halide, an acetonate, a carbonate, a sulfate, an acrylate or an alcoholate of the formula OR 2 where R 2 is an alkyl group of 1 to 10 carbon atoms, and x is 1, 2 or 3 .
• the organosilane corresponds to the following formula (II):
• the organosilane may, in general, be chosen in particular from alkoxy (1 to 10 C) silanes, for example methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and the like.
• the complexing organic compound may be chosen from carboxylates of formula R 3 COO- in which R is a linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, or a phenyl group; the ⁇ -diketonates and ⁇ -diketonate derivatives, for example of formula R 4 COCHCO-R 5 , in which R 4 and R 5 are independently selected from a linear or branched alkyl group of 1 to 30 carbon atoms, preferably from 1 to 10 carbon atoms, or a phenyl group; the phosphonates, for example chosen from the group consisting of R 6 PO (OH) 2 , R 7 PO (OR 8 ) (OH) or R 9 PO (OR 10 ) (OR 11 ) in which R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are identical or different alkyl groups, linear or branched, having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms
• soluble in these solvents is generally meant that the polymer is soluble at 1 to 99% by weight based on the total mass of the solution.
• the organic polymer may in particular be chosen from polyvinyl polymers, for example polyvinyl alcohol, polyvinylpyrrolidone, and polyvinylbutyral; the polysiloxanes, for example polydimethylsiloxane; polymethacrylates; polyacrylates; polyesters; polyether esters; polyurethanes; fluorinated polymers and copolymers such as polyvinylidene fluoride and the PVdF / HFP copolymer or polytrétrafluoroéthylènes, such as Teflon ® AF; polystyrenes; polycarbonates; polysilazanes; polyvinylcarbazoles; polyphosphazenes; and the mixtures consisting of previously mentioned polymers.
• polyvinyl polymers for example polyvinyl alcohol, polyvinylpyrrolidone, and polyvinylbutyral
• the polysiloxanes for example polydimethylsiloxane
• the polymer is inorganic, it is generally soluble species and polymerized from organometallic precursors whose organic part is generally branched and comprises for example vinyl functions, acrylates, perfluorinated, like 3.3, 3- trifluoropropyltrimethoxysilane.
• the material according to the invention is preferably in the form of a thin layer with a thickness generally from 1 to 1000 nm, preferably from 10 to 500 nm, more preferably from 50 to 100 nm.
• This thin layer is preferably an "optical" thin layer.
• This term is defined below.
• this thin layer is a thin transparent layer in a range of wavelengths between the ultraviolet and the near infrared, including the visible spectrum and this layer is a layer of "optical quality" as defined above.
• the material according to the invention can also be in the form of a layer colored, for example an absorbent colored thin layer in the case for example where the oxide or the oxyhydroxide is colored.
• the invention furthermore relates to a process for the preparation of a solution of an organic-inorganic (hybrid) composite material, as described above, in an apolar, aprotic solvent in which the following successive steps are carried out: of a suspension (1) or sol, of colloidal particles of at least one inorganic compound selected from oxides and oxyhydroxides of metal or metalloid, prepared by a hydrolysis-condensation process, in a protic or polar solvent (2 ); - Mixing the suspension (1) with an organic compound (3) capable of functionalizing the surface particles, said organic compound being optionally dispersed in the same protic solvent (2), to obtain a suspension (4); reaction, grafting of the organic compound
• suspension can also be used to denote the solution (10) because at the microscopic scale it is a suspension that macroscopically has the appearance of a solution.
• suspension (4) could be called "solution”.
• the invention furthermore relates to a process for the preparation of a hybrid material, an organic-inorganic composite in which a solution of an organic-inorganic (hybrid) composite material is prepared in an apolar solvent, aprotic by the method described herein. above, this solution is applied to a substrate and the solvent is evaporated from the solution.
• the hybrid material, organic-inorganic composite thus prepared is in the form of a thin layer whose thickness has already been defined above on a substrate.
• this material is transparent and the substrate is also preferably transparent.
• the process according to the invention for preparing a solution of an organic-inorganic (hybrid) composite material, and the subsequent method according to the invention for preparing a hybrid material, an organic-inorganic composite comprises a series of specific steps that has never been described or suggested in the prior art.
• the process according to the invention allows, surprisingly, the accounting of an inorganic phase, mineral, prepared in protic medium, apolar, for example aqueous or aqueous-alcoholic with an organic phase comprising a solvent or a polymeric solution, which is essentially or even exclusively aprotic, apolar. Consequently, nanoparticles of oxides or oxyhydroxides of metals prepared with all the known advantages of the sol-gel process in protic medium, polar, can be implemented with all kinds of solvents and not only with the polar, protic solvents, and also with all kinds of polymers and no longer only with polymers soluble in protic polar solvents.
• the polymer which is solubilized in the solvent (6) is an already synthesized polymer and it is this already formed polymer which is mixed with the solvent.
• the polymer is not prepared by in situ polymerization from soluble monomers as in document [6] which, again, considerably widens the range of polymers that can be implemented.
• the grafting on the surface of the inorganic nanoparticles of a ring of organic molecules ensures the stabilization of these in an organic medium which is a solvent or a polymeric solution totally different from the polar medium, protic in which they were initially prepared.
• a suspension which is a stable organic-inorganic hybrid solution over time, generally lasting one or more months, for example from 1 to 6 months.
• stable solution within the meaning of the invention, generally means that no phase separation is observed, that there is no precipitation or decantation of a solid phase, no flocculation, aggregation or demixing.
• the stability induces the preparation of a layer, for example thin, with, for example, constant optical properties, in particular as regards the refractive index.
• the polymer is generally soluble in apolar solvents, aprotic but not in the polar solvents, protic in which the inorganic nanoparticles have been prepared and thanks to the process according to the invention, a suspension is obtained, a stable solution in which coexist in a completely compatible manner. the nanoparticles, the apolar solvent, aprotic and the soluble polymer in the latter.
• the polymer surrounds the particles, which are themselves already functionalized, grafted, stabilized, and it is thus in the presence of a composite hybrid system which has the advantage to behave as a conventional medium and which can be easily implemented by a conventional, proven liquid-phase deposition method.
• the processes according to the invention also allow: the deposition in the form of a coating with a controlled organic / inorganic composition, advantageously transparent from the ultraviolet to the near infrared, having excellent optical quality (generally without absorption or diffusion); the control of the refractive index of the deposited hybrid films by the composition of the solution defined by the proportion of organic phase relative to the inorganic phase.
• the higher the proportion of inorganic phase the higher the refractive index.
• FIG. 2 is a graph which compares the percentage in number (Number (%)) of functionalized particles (A1OOH / TFP) having a determined hydrodynamic diameter (in nm) respectively in the suspension (7) whose solvent is 2-butanone and in the suspension (5), the solvent of which is methanol 2, prepared in Example 1; the black bars A (left in each pair of bars) concern the suspension in methanol and the white bars B (on the right in each pair of bars) concern the suspension in 2-butanone.
• FIG. 3 is a transmission electron microscopy (TEM) shot of AlOOH before grafting of trifluoropropyltrimethoxysilane (TFP), the scale shown in the figure represents 50 nm.
• TEM transmission electron microscopy
• Figure 4 is a transmission electron microscopy (TEM) shot of AlOOH after grafting trifluoropropyltrimethoxysilane (TFP), the scale shown in the figure represents 50 nm.
• TEM transmission electron microscopy
• FIG. 6 is a TEM (Electron Transmission Electron Microscopy) micrograph of ZrO 2 before grafting of trifluoroporopyltrimethoxysilane (TFP), the scale indicated in the figure represents 50 nm.
• Figure 7 is a transmission electron microscopy (TEM) ZrO 2 after grafting trifluoropropyl trimethoxysilane (TFP), the scale shown in the figure represents 50 nm.
• TEM transmission electron microscopy
• FIG. 8 represents the UV and visible spectra of a stack comprising on a substrate, six pairs of layers; each pair comprising a silica layer and a TFP grafted ZrO2 hybrid material layer, curve A is the spectrum of the bare substrate, spectrum B is the simulated spectrum of the stack [Si0 2 / Zro 2 -TFP] 6 on the substrate, and spectrum C is the experimental spectrum of the [SiO 2 / ZrO 2 ⁇ TFP] stack on the substrate.
• Figure 9 is a photograph of the mirror stack prepared in Example 3.
• the first step of the process according to the invention for preparing a solution of the organic-inorganic hybrid material in an apolar aprotic solvent consists in preparing a suspension (1).
• inorganic compound colloidal particles.
• colloidal particles have already been defined above, as regards, in particular, their nature, their structure, or their size.
• the polar or protic solvent (2) of the suspension (1) has also been defined above.
• a preferred polar or protic solvent is methanol.
• the colloidal particles are prepared in a polar or protic solvent and may remain in the same polar or protic solvent where they have been prepared to give the suspension or sol of particles (1) in the same polar or protic solvent (2).
• the polar solvent, protic (2), of the solution (1) such as methanol may also be different from the polar solvent, protic such as water wherein the particles have been prepared.
• the water used for synthesis by methanol can be replaced, for example by dialysis.
• the polar or protic solvent in which the colloidal particles are prepared which is identical to or different from the solvent (2) of the suspension (1), is chosen from the polar, protic solvents mentioned above.
• the suspension (4) is obtained by adding to the solution (1) a molecular compound (3) based on organosilane or a complexing molecular compound.
• the molecular compound has already been described in detail above.
• the molecular compound may be optionally dispersed and / or dissolved in a solvent of the same nature as the solvent (2), preferably in the same solvent (2) as that of the solution (1).
• the organic molecular compound (3) may be added in a proportion of 1 to 99% by weight, for example 5 to 50% by weight relative to the mass of inorganic compound selected from oxides and oxyhydroxides of metal or metalloids.
• the grafting, the reaction, of the organic compound (3) on the surface of the particles (2) are generally carried out by a heat treatment, for example by refluxing the solvent (2) of the suspension (4), leading to functionalization of the particles.
• the aprotic apolar organic solvent (6) is exclusively an anhydrous organic solvent, aliphatic or cyclic, saturated or unsaturated having one or more alkyl groups of 1 to 30 carbon atoms or one or more aromatic groups such as phenyl groups and may be chosen in particular from ketones, for example acetone, 2-butanone ; tetrahydrofuran; 1,4 dioxane; toluene; styrene; cyclohexane; Acetonitrile; amides; fluorinated solvents, such as Galden ® HT110; the ethers; esters and mixtures of the solvents mentioned above.
• Solvent such as Galden ® HT110
• the organic solvent (6) is 2-butanone, tetrahydrofuran or 1,4-dioxane.
• the exchange of the protic solvent (2) of the suspension (5) with the apolar, aprotic organic solvent (6) can be carried out by azeotropic distillation or by dialysis of the suspension (5) to the organic solvent (6) to obtain the suspension (7) in which the nanoparticles are stabilized in the organic solvent (6).
• the molecular compound (3) serves essentially to ensure the stabilization of the colloids in the organic solvent (6).
• the amount of molecular organic compound (3) introduced into the organic-inorganic hybrid solution makes it possible to control the stability of it. This amount is generally from 5 to 50% by weight relative to the weight of the inorganic compound.
• the organic polymer is solubilized in the solvent (6) to obtain a polymeric solution (9).
• the organic polymer may be chosen from the abovementioned polymers, preferably from polymers soluble in apolar aprotic solvents.
• the solubilization of the polymer in the solvent (6) is generally carried out as follows:
• this agitation is a mechanical and / or magnetic stirring, and it is possible to carry out an ultrasonic treatment during or after said stirring.
• the weight ratio organic polymer / inorganic compound (that is to say oxide or oxyhydroxide) is generally between 1 and 99%, preferably between 5 and 50%, for example 10%.
• the invention also relates, as already mentioned above, to a process for preparing the hybrid material, an organic-inorganic composite which has been described in detail above, in which a solution of a composite material is prepared ( hybrid) organic-inorganic, in an apolar solvent, aprotic by the method described above, is deposited, applied, this solution on a substrate and the solvent is evaporated from the solution.
• the hybrid material, organic-inorganic composite thus prepared is in the form of a thin layer on a substrate
• thin layer it has been seen above that generally meant a layer having a thickness of 1 to 1000 nm, preferably 10 to 500 nm, more preferably 50 to 100 nm.
• This layer is preferably a transparent layer but it can also be a colored absorbent layer.
• Transparency within the meaning of the present invention generally means that this material, this layer has a transparency to the radiation of a wavelength between the ultraviolet and the near infrared that is to say for example 150 at 2000 nm.
• the method for preparing the hybrid organic-inorganic composite material comprises the following successive steps: cleaning the surface of the substrate; rinsing and drying the surface of the substrate; depositing the solution (10) of organic-inorganic hybrid material (10) on the substrate to form a uniform layer of hybrid organic-inorganic material solution. evaporating the solvent to form a uniform layer of inorganic hybrid material.
• Substrate any substrate, organic support, or inorganic, including metallic, such as those to be described later or any active layer or adhesion promoting, deposited on said substrate.
• the substrate is a flat substrate or a substrate having a small curvature, for example a spectacle lens, but the method according to the invention makes it possible to coat any substrate regardless of its shape.
• substrate also includes substrates comprising a base substrate (e.g., glass itself) and a coating or treatment.
• the substrate according to the invention may be any material, but it is generally a substrate of a transparent material.
• transparent material is meant a material which can be traversed by light rays of wavelengths in the spectral range of interest, as defined above, for example, the visible spectrum.
• the substrate if it is not transparent may also be a reflective material, for example a metal such as gold.
• substrate also includes substrates comprising a base substrate (e.g., glass itself) and a coating or treatment.
• the substrate may be an organic substrate or an inorganic substrate, including metallic substrate.
• organic substrate more specifically denotes a plastic substrate, for example one of those chosen from polyacrylates, poly (methyl methacrylate) (PMMA), acetobutyrates, cellulose acetates, diallylglycol carbonates, polyurethanes, ABS, polycarbonates, polyallyl carbonates and polyamides.
• PMMA poly (methyl methacrylate)
• acetobutyrates cellulose acetates
• diallylglycol carbonates polyurethanes
• ABS polycarbonates
• polyallyl carbonates polyamides
• inorganic substrate more precisely covers a mineral substrate, that is to say, for example amorphous or even crystalline materials and in particular silica, silicon, glasses, such as borosilicate or soda-lime glasses, fluorophosphates and phosphates, and metals in the case of reflective substrates.
• plastic substrates are above all cheaper, more easily modulated, lighter and less fragile to shocks.
• their use preferably requires the presence of an interposed layer called interface layer or varnish between the organic substrate and the first layer deposited, ensuring good accounting for this interface.
• the substrate is generally of a material selected from polished optical and ophthalmic lenses.
• Optical and ophthalmic lenses may be chosen from organic glasses, in a material as defined above; or among mineral glasses, such as borosilicate glasses, defined above and high-refractive glasses, that is to say generally from 1.7 to 1.9.
• the substrate for example mineral glass, may be provided with no coating.
• the cleaning of the substrate in particular in the case of a glass substrate, may be carried out using one or more cleaning and treatment liquids chosen, for example, from alcohols, acids, soaps, ketones 'water.
• this cleaning can be carried out using acetone, an aqueous solution of 1% hydrofluoric acid, deionized water, absolute ethanol, preferably successively in this order.
• the rinsing of the substrate in particular in the case of a glass, can be carried out with deionized water.
• the drying of the substrate can be carried out with absolute ethanol.
• the deposition of the solution (10) in particular on a substrate may be carried out by any of the techniques conventionally used for depositing a solution on a substrate such as, for example, spraying (or "spray-coating" in the English language). spin-coating in English), drop-coating in English, dip-coating in English, and so on.
• laminar flow coating or “laminar flow coating” or “meniscus-coating” in English
• spreading or “soak-coating” in English
• roll coating or “roll-to-roll process”
• coating with a horizontal knife or “tape casting” in English
• brushing or “painting-coating” in English
• the solvent present in the solution is removed by evaporation, it can be done naturally in the open air or can be facilitated, for example by applying a gas stream, by thermal or radiative heating provided that the temperature does not alter the solution or the underlying substrate or by mechanical means such as the rotation of the substrate during deposition by centrifugal coating.
• Residual solvent may remain in the proportions in the layer, for example, in a proportion of less than 2% by weight of the mass of the layer.
• optical material comprising a substrate covered by at least one layer, preferably a thin layer of organic-inorganic hybrid material as defined above.
• optical material is generally meant in the sense of the invention a material exerting an action on a light beam and in particular on the trajectory thereof for example by deviating, polarizing, reflecting, absorbing,
• Such a material has, for example, antireflection properties or reflective properties, or even polarizing, absorbing, attenuating properties.
• the refractive index of the layer of organic-inorganic hybrid material can be adjusted by choosing the metal oxide or oxyhydroxide in the composition of the colloidal nanoparticles, the nature of the organic compound of functionalization, the nature of the polymer, the molar ratio organic compound of functionalization / oxide or oxyhydroxide of metal.
• low, medium and high refractive index should generally be interpreted to mean that the index is less than about 1.4; from about 1.4 to about 1.6; and greater than about 1.6.
• the layer of organic-inorganic hybrid material may in particular be a high refractive index layer formed for example by a layer of zirconium oxide functionalized on the surface by TFP (trifluoropropylmethoxysilane).
• the optical material may comprise, in addition to the hybrid organic-inorganic layer, for example with a high refractive index, at least one layer chosen from: an adhesion promoter layer; a low refractive index layer; a medium refractive index layer; a bonding agent layer; a layer of a coupling agent; an anti-abrasive layer.
• the optical material may be a reflective material comprising on a substrate at least one stack of a layer of hybrid organic-inorganic material with a high refractive index on a low refractive index layer.
• the low refractive index layer may be for example a colloidal silica layer and this optical material may comprise from 1 to 50, for example 6 of these stacks.
• a thin layer of organic-inorganic hybrid material comprising 3,33 trifluoropropyltrimethoxysilane (TFP) functionalized aluminum oxyhydroxide nanoparticles and a PVdF-HFP copolymer is prepared.
• TFP 3,33 trifluoropropyltrimethoxysilane
• PVdF-HFP copolymer a PVdF-HFP copolymer
• a colloidal suspension (1) of aluminum oxyhydroxide nanoparticles (AlOOH) is prepared.
• the particles synthesized in water are dispersed in methanol by dialysis, until a totally methanolic sol at 5% is obtained. oxide mass.
• the molecular compound (3), 3,3,3-trifluoropropyltrimethoxysilane (TFP), is then added to the solution (1).
• the molar ratio organosilane / oxide may be between 0.05 and 5 and more precisely between 1 and 3, for example 2.
• the suspension (4) thus prepared is maintained in magnetic stirring for 30 minutes and stored under an inert atmosphere of nitrogen or argon.
• This suspension (4) is refluxed with methanol for 16 hours, under an inert atmosphere of nitrogen or argon.
• the suspension (5) in methanol thus obtained remains stable for at least two months.
• FIG. 1 makes it possible to demonstrate a slight increase in the hydrodynamic diameter of the particles after functionalization.
• a solvent transfer by azeotropic distillation makes it possible to disperse the nanoparticles grafted in the solvent (6), the 2-butanone, and to obtain the solution (7).
• FIG. 2 shows that, during the transfer to the organic solvent (2-butanone) by azeotropic distillation, the size of the nanoparticles expressed by the hydrodynamic diameter remains approximately constant, it passes in effect from 39 nm to 38 nm in average hydrodynamic diameter, c that is, the Functionalization of the surface of the oxide allows a good stabilization in organic medium without aggregation.
• a polymeric solution (9) is produced by solubilizing a PVDF / HFP copolymer (8) dissolved in an organic solvent (6): 2-butanone at a concentration of 3%.
• the hybrid organic-inorganic solution is produced by solubilizing a PVDF / HFP copolymer (8) dissolved in an organic solvent (6): 2-butanone at a concentration of 3%.
• (10) is obtained by mixing the colloidal suspension (7) and the polymeric solution (9).
• the proportion of polymer is between 10 and 30% of polymer relative to the dry mass of oxyhydroxide and organosilane.
• the solution (10) is stirred for 15 minutes by magnetic stirring followed by a sonication treatment of 30 minutes.
• the deposit of the solution (10) is carried out by spin-coating.
• the substrate is a fused silica substrate with a diameter of 50 mm.
• the substrate is cleaned as has already been described above, and the substrate is rotated at a speed of 500 tr.min "1 approximately.
• the deposition is carried out with approximately 1 mL of solution (10).
• FIG. 5 gives the value of the transmission (%) as a function of the wavelength ( ⁇ ) for a substrate coated with a material according to the invention, prepared according to the present example, which is a hybrid material comprising TFP-functionalized AlOOH nanoparticles, and a PVdF / HFP copolymer at various percentages by weight (10, 20, 30 and 40%); for an uncoated substrate (bare substrate); and for a substrate coated with a thin layer of AlOOH functionalized by TFP.
• the invention makes it possible, as shown in FIG. 5, to obtain a hybrid organic-inorganic thin film without optical loss by absorption and / or diffusion and in a wide range of wavelengths.
• a thin layer of organic-inorganic hybrid material comprising colloidal zirconium oxide nanoparticles functionalized with 3,3,3-trifluoropropyl-trimethoxysilane (TFP) is prepared.
• a colloidal suspension (1) of zirconium oxide nanoparticles is prepared.
• the protocol used for the synthesis of ZrO 2 nanoparticles is described in reference [17] and the molar proportions used are as follows: ## EQU1 ## W2U ZrOC12 Urea
• the particles synthesized in water are dispersed in methanol by dialysis, until a completely methanolic sol at 5% oxide mass is obtained.
• Molecular compound (3), 3,3,3-trifluoropropyltrimethoxysilane (TFP) is then added to solution (1).
• the molar organosilane / oxide ratio may be between 0.05 and 5 and more precisely between 0.1 and 0.5, for example 0.3.
• the functionalization of the nanoparticles makes it possible to limit the aggregation that we can observe on the plate of FIG. 6. This functionalization thus makes it possible to obtain nanoparticles whose dispersion is possible in various types of organic solvents.
• a reflective coating composed of a stack of high and low refractive index layers is prepared.
• the low refractive index layer is based on colloidal silica and the high refractive index layer is based on the hybrid material prepared in Example 2.
• Colloidal silica is synthesized on the basis of the protocol described in reference [18], in order to obtain a 1% by weight solution in ethanol.
• the hybrid organic-inorganic material is synthesized as described previously in the example
• a coating having 90% reflection at ⁇ 600 nm was obtained by centrifugal coating at from the following stack: Substrate / [Si ⁇ 2 / Zr ⁇ 2-TFP] 6 (6 pairs of stacked SiO 2 / ZrO 2 -TFP layers.
• the layer of this colloidal silica is obtained by centrifugal coating at a speed of 500 rpm. That of the hybrid material is obtained in two passes at a speed of 450 rpm. A heat treatment of 15 minutes at 120 ° C. was carried out between each layer with low and high refractive index.
• the V / Visible spectrum of this stack is shown in FIG. 8.
• Figure 9 shows a photograph of a homogeneous coating on the entire substrate and made from the method described.
• the realization of such a reflective stack shows that the nature of the organic-inorganic hybrid layer with high refractive index is of very good optical quality.
• the above examples show that the process for producing the organic-inorganic hybrid material is possible from oxides of different natures. These materials then allow the realization of transparent coatings with adaptable refractive index, to enter for example in the composition of reflective coatings.

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