Classifications

• • 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
  • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
  • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing 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
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
  • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/70—Properties of coatings
  • C03C2217/75—Hydrophilic and oleophilic coatings

Definitions

• TITLE Sol-gel composition curable under the effect of UV radiation to obtain a hydrophobic coating
• the present invention relates to the hydrophobic treatment of a substrate, in particular consisting of a glass material, a ceramic, glass ceramic, etc.
• the glazing according to the invention is preferably glass glazing. They are used, in particular, in the aeronautical, railway or automobile field. They can also be used in the building sector or in the field of interior fittings such as, for example, decorative panels, for furnishings, household appliances (refrigerator doors, oven doors, display cases) or as wall panels. shower, etc.
• This type of treatment aims to reduce the initial wettability of a substrate, so as to give it so-called anti-rain properties.
• wettability conventionally denotes the property according to which polar liquids, in particular water, adhere to the surface of a substrate and form a continuous film thereon.
• hydrophobicity The property of non-wettability of a substrate in water, more commonly referred to as hydrophobicity, is all the higher as the contact angles between a polar liquid and this substrate are high, for example at least 90 ° for the water.
• the liquid then tends to flow easily, in the form of drops, on the substrate, by simple gravity if the substrate is tilted, or under the effect of aerodynamic forces in the case of a moving vehicle.
• Agents known to confer this hydrophobicity property are, for example, fluorinated alkylsilanes as described in patent applications EP 0 492 417, EP 0 492 545 and EP 0 672 779. According to these documents, this layer can be obtained by applying on the surface of a substrate a solution containing fluorinated molecules in a non-aqueous organic solvent.
• Common hydrophobic compounds are, in particular, alkylsilanes in which the alkyl group has at least one fluorinated end and preferably perfluorinated, that is to say consisting of an F3C- (CF2) n - group, in which is not a positive or zero integer as described in application EP799873A1 or W02004 / 084943.
• alkylsilanes in which the alkyl group has at least one fluorinated end and preferably perfluorinated, that is to say consisting of an F3C- (CF2) n - group, in which is not a positive or zero integer as described in application EP799873A1 or W02004 / 084943.
• Patent EP 944 687 more particularly describes anti-rain coatings produced by the liquid process and comprising an underlayer or priming layer based on sol-gel silica obtained from a precursor of the Si (OEt) 4 or SiCU type and a hydrophobic layer of fluorinated silane comprising perfluoroalkylsilane groups (F3C- (CF2) m- (CH2) n).
• hydrophobic compounds such as perfluoropolyethersilane comprising hydrophobic perfluoropolyether groups such as the compound Fluorolink S 10® (perfluoropolyether-triethoxysilane) marketed by the company Solvay or even compounds of the alkylsilane type whose group comprises a long linear carbon chain and unsubstituted as the compound 1,2-Bis (trimethoxysilyl) decane marketed under the reference SIB 1829.0 by the company Gelest.
• fluorolink S 10® perfluoropolyether-triethoxysilane
• the inorganic layers usually obtained by the sol-gel route are produced from hydrolysed solutions prior to deposition on the substrate: a layer of silica obtained by the conventional sol-gel route (called sol-gel silica in the field) involves a first step of hydrolysis of the solution, with in most cases a rise in temperature ( ⁇ 80 ° C), a second maturing step (which corresponds to a first condensation of SiOH groups in Si-O-Si bond) but which must be limited and a third step, that of deposition, in order to ensure good optical and mechanical properties of the layer. The third step must be carried out shortly after the second, so that the coating ultimately exhibits the best qualities of mechanical resistance and adhesion to the substrate.
• sol-gel silica in the field involves a first step of hydrolysis of the solution, with in most cases a rise in temperature ( ⁇ 80 ° C), a second maturing step (which corresponds to a first condensation of SiOH groups in Si-O-Si bond) but which must be limited and a third step, that of de
• sol-gel route conventionally used is therefore characterized by low cost, but the hydrolysis step prior to deposition and the limited pot life leads to steps for manufacturing the solution at each production shift and throwing the remaining solutions at the disposal. end. This represents a cost in terms of production time and raw material.
• the present invention relates firstly to compositions which ultimately provide hydrophobic abrasion-resistant and chemically resistant coatings.
• such mechanical and chemical resistance typically allows them to meet the specifications currently imposed by the automotive industry for such coatings, both in terms of resistance to abrasion and to salt corrosion.
• the present invention relates to a composition whose shelf life from its manufacture to its application on the substrate which it covers is substantially increased compared to solutions of the prior art.
• the invention relates to a composition which can be crosslinked / curable under the effect of UV radiation, for obtaining a hydrophobic coating on a glass substrate, said composition being characterized in that it comprises, and preferably consists essentially of:
• oligomer between 80% and 98% by weight, preferably between 80% and 95% by weight, in particular between 85% and 95% of at least one oligomer of an organo-functional compound of a metal A, the oligomer comprising the following sequence: [(RO) 2AO] n
• - A is chosen from Si, Ti, Zn, Zr, Al, Ce, V, Nb or Y or an InSn alloy;
• - R is a linear, branched or aromatic carbon chain, preferably linear, preferably in which the number of carbons is between 1 and 6, limits included, more preferably in which the number of carbons between 1 and 3 limits included ,
• - n is between 2 and 20, preferably between 4 and 10,
• c) between 0.5 and 15% by weight, preferably between 1 and 10% by weight, of a compound comprising a hydrophobic group.
• the hydrophobic coating finally obtained preferably comprises a silica matrix obtained by the sol-gel route (or sol-gel matrix).
• sol-gel silica matrix is conventionally understood to mean a silica obtained by sol-gel reaction, and consisting essentially of a material exhibiting a three-dimensional chain of Si-O-Si bonds in the sense described in the reference work “Sol-Gel Science”. , The physics and Chemistry of Sol-Gel processing, CJ Brinker et al., Academy Press, 1990.
• hydrophobic compound or compound comprising a hydrophobic group is understood to mean in particular a material making it possible to obtain a solid surface whose contact angle is greater than 90 °, from the surface tension values measured according to the method of Owens, Wendt , Rabel and Kaelble (OWRK).
• OWRK Kaelble
• a surface is hydrophobic if its contact angle thus determined is greater than 90 °.
• a composition according to the invention is therefore hydrolyzable and then crosslinkable by condensation under the effect of UV radiation which activates the photoacid compound, allowing the hydrolysis step and the formation of condensable products during the crosslinking reaction.
• a PAG photoacid compound is well known a compound which, under the effect of ultraviolet (UV) radiation, dissociates into at least two elements, one of which is a strong acid. This strong acid then catalyzes, according to the invention, the polymerization of the oligomer of the organo-functional compound described above and its crosslinking into a sol-gel silica matrix.
• the photoacid compound can be an onium compound, preferably chosen from diazonium, iodonium or sulphonium compounds or an organometallic complex such as a metallocene salt, in particular a ferrocene salt.
• PAGs which can be used according to the present invention are for example described in paragraphs [0109] to [01 13] of the publication EP2850140B1.
• the compounds comprising a hydrophobic group according to the invention are in particular fluorinated silanes.
• Fluorinated silanes comprising perfluoroalkylsilane groups for example of the (F3C- (CF2) m- (CH2) n) type, or alternatively perfluoropolyethersilane comprising hydrophobic perfluoropolyether groups such as the compound Fluorolink S 10, can be used more particularly according to the invention.
• ® perfluoropolyether-triethoxysilane sold by the company Solvay.
• compositions according to the invention are compounds of the alkylsilane type, the group of which comprises a long linear and unsubstituted carbon chain, an example of which is 1,2-Bis (trimethoxysilyl) decane, sold on the market. under the reference SIB 1829.0 by the company Gelest.
• the compound comprising a hydrophobic group may or may not be bound to the sol-gel matrix finally obtained. If they exist, such bonds can in particular be covalent.
• A is silicon Si, titanium Ti, or Zinc Zn, more preferably A is silicon Si.
• the oligomer is a polysiloxane.
• the oligomer is chosen from polydimethoxysiloxane PDMOS [(CH 3 0) 2 Si0] n or polydiethoxysiloxane PDEOS [(C2HsO) 2SiO] n and mixtures thereof.
• the photoacid compound is an onium compound, preferably chosen from diazonium, iodonium or sulphonium compounds.
• the photoacid compound is diphenyl iodoniumhexafluorophosphate
• the hydrophobic group is chosen from perfluoroalkyl groups, perfluoroether groups or alkyl groups comprising a linear carbon chain of at least eight consecutive carbon atoms.
• the compound comprising a hydrophobic group is an alkoxysilane, in particular an ethoxysilane.
• the compound comprising a hydrophobic group is a perfluoroalkylsilane.
• the compound comprising a hydrophobic group is a perfluoropolyethersilane, in particular a perfluoropolyether-triethoxysilane
• the compound comprising a hydrophobic group is a
• - m 0 to 15, preferably 5 to 9;
• n 2
• - p 0, 1 or 2, preferably 0 or 1, very preferably 0;
• R is an alkyl group or a hydrogen atom
• - X 3 is a hydrolyzable group such as a halide group or preferably an alkoxy group.
• the compound comprising a hydrophobic group is perfluorodecyltriethoxysilane CF3 (CF2) 7 (CH2) 2Si (OC2Hs) 3 or perfluorodecyltrimethoxysilane CF3 (CF2) 7 (CH2) 2Si (OCH3) 3.
• composition is diluted in an aprotic solvent such as ethyl acetate.
• the invention also relates to a process for depositing a coating with hydrophobic properties on a glass substrate from a composition as described above.
• Such a process comprises the following steps: a) a composition according to one of the preceding claims is prepared, b) said composition is applied to said glass substrate in a layer with a thickness of between 0.01 and 3 micrometers, preferably between 0, 1 and 1 micrometers,
• the layer is subjected to a treatment by UV radiation until at least partial crosslinking, preferably total, to obtain a hydrophobic coating.
• the invention relates to a glass article comprising a glass substrate, on a surface of which is deposited a coating with hydrophobic property obtained from the composition described above.
• Such a hydrophobic coating comprises:
• a sol-gel matrix preferably a sol-gel silica, comprising and preferably consisting essentially of a mineral obtained by a sol-gel reaction
• the hydrophobic compound comprises a fluorinated alkyl group, in particular a perfluoroalkyl group or a perfluoroether group, or in which the hydrophobic compound comprises an alkyl group comprising a linear carbon chain of at least eight consecutive carbon atoms.
• a glazing according to the invention may consist of a product whose outer surface, most often constituted by a glass material, ceramic, glass-ceramic or a natural mineral material, is provided at least in part with a hydrophobic coating as described above or obtained from a composition and / or a process as described above.
• a product according to the invention is, for example, a monolithic, laminated or multiple glazing.
• glazing consisting of a single sheet of glass
• laminated glazing a stack of several sheets integral with one another, for example sheets of glass or of plastic material fixed to each other by means of adhesive layers of polyvinyl butyral, polyurethane, etc.;
• multiple glazing an assembly of disjointed sheets, that is to say in particular separated from each other by layers of air.
• the advantage of the hydrophobic / oleophobic coating of the invention for this type of products is twofold. First of all, it allows the flow of water drops or other liquid on vertical or inclined surfaces, possibly under the effect of aerodynamic forces, for example in the case of a moving vehicle. In addition, these dripping drops absorb dirt and carry it away. Visibility through the glazing is improved to such an extent that it is possible in certain cases to dispense with cleaning devices (window washers, windshield wipers).
• glazing for transport vehicles (automobile side windows, aviation or automobile windshields) or for buildings;
• - as a piece of furniture, in particular as a mirror, storage shelf, shelf for household appliances such as a refrigerator, shower cabin element, partition.
• an initial composition which comprises an oligomeric sol-gel silica precursor, a precursor of a fluorinated or silicone hydrophobic molecule (in particular a fluorosilane, fluoropolymer, silicone polymer) and of a PAG photoacid compound. in the sense described above.
• a first formulation is produced with an amount of 96% by weight of PDMOS (poly (dimethoxysiloxane) as precursor of sol-gel silica, 1% by weight of Diphenyliodonium hexafluorophosphate as photo-acid compound (PAG) and 3% weight of perfluorodecyltriethoxysilane CF3 (CF2) 7 (CH2) 2Si (OC2H5) 3 (or SÎF7E) as the hydrophobic precursor.
• PDMOS poly (dimethoxysiloxane) as precursor of sol-gel silica
• PAG photo-acid compound
• PAG photo-acid compound
• perfluorodecyltriethoxysilane CF3 (CF2) 7 (CH2) 2Si (OC2H5) 3 or SÎF7E
• a 10 cm 2 clear glass substrate is cleaned by ceroxing: the surface of the glass is abraded using a felt pad impregnated with an aqueous solution of Cerox at 20 wt%. Then the glass is rinsed with distilled water.
• the formulation is then filtered at 1 micron to remove any residues of undissolved PAG.
• the deposit on the glass is carried out by centrifugal coating (spin coater) at a speed of 1500 rpm 1 , with an acceleration of 1000 rpm 2 and for a period of 30 seconds.
• the layer is obtained by crosslinking under UV by illumination with a UV lamp.
• the crosslinking can be done with any type of lamp possible, in particular of the Hg vapor, Hg galium microwave or LED type.
• the hydrolysis and condensation steps are then carried out successively under UV activation.
• the glass then passes under UV with a lamp power set at 100% and a passage speed of 10m / min.
• Example 4 A comparative sample according to the prior art (Example 4) prepared according to the teaching of Example 5A of publication EP 799873A1 was also prepared. II - Evaluation of samples
• the abrasion resistance obtained by measuring the residual contact angle of water on the sample after the hydrophobic coating has undergone abrasion according to the Opel® friction test, carried out on the samples with a felt of Hl hardness, a load of 0.4 kg / cm 2 on an area of 1.5 cm 2 , with a translation speed of 50 cycles / minute and a rotational speed of 6 revolutions / minute.
• the contact angle is measured after 10,000 cycles and compared to the initial angle.
• a homogeneous and transparent layer having a thickness of between about 10 nm and up to 3 microns without cracks, with an initial contact angle of between 90 ° and 130 °, preferably between 100 ° and 120 ° and a hysteresis (difference between the angle of advance and the angle of retreat) of between 20 ° and 40 °, preferably between 25 ° and 35 °.
• Example 1 for the hydrophobic layer finally obtained, an initial contact angle of 12 °, a hysteresis of 37 ° for a thickness of 0.87 micrometer is measured.
• the glazing according to Examples 2 and 3 have substantially identical characteristics.
• Comparative Example 4 has an initial contact angle of 1 10 °, a hysteresis of 30 ° and a thickness of 12 nm (including priming).
• the transparency characteristics of the glazing after deposition of the hydrophobic layer according to Example 1 are given in Table 2 below:
• the BSN test is carried out as described above for 7 days.
• a contact angle of 102 °, slightly reduced compared to its initial value, is measured on the glazing according to Example 1 after the test.
• the contact angle measured under the same conditions for the comparative sample according to Example 4 is 104 °.
• the UV-crosslinked hydrophobic layer according to the invention therefore has hydrolytic resistance substantially equivalent to the hydrophobic layer according to the prior art and in particular meets automotive standards.
• composition according to the invention is its possible storage over long periods of time before it is deposited on the glass substrate and its crosslinking, triggered exclusively by UV radiation.
• the hydrophobic layers obtained by depositing and curing a composition aged from a few days to several hundred days exhibit properties substantially identical to those obtained without aging.
• the pot life of the composition according to the invention is therefore clearly greater than a sol-gel formulation comprising a hydrolysis step beforehand according to the prior art (as a reminder only 4 hours for the composition according to example 4).
• the hydrophobic layers obtained from the compositions according to the invention have an initial contact angle greater than 100 ° and are transparent.
• the initial composition making it possible to obtain the hydrophobic coating can be stored for several weeks, or even several months, without noticeable consequence on the properties of the hydrophobic layer finally obtained after curing / crosslinking by UV radiation, which is an essential advantage in the domain because the deposition of the hydrophobic layer can be done well after the constitution of the initial composition, and in particular on the site of production of the hydrophobic glazing, which can be different from the site of manufacture of the initial composition.
• the precursor of the hydrophobic molecule is integrated into the finally obtained solo-gel silica matrix and is not simply present on the surface of the coating as in the previous solutions, which helps to ensure an extended service life. of the hydrophobic property.
• any type of compound known for its hydrophobic properties can be used according to the invention as a hydrophobic agent. within the UV crosslinked layer.
• the implementation of the present invention thus ultimately allows a reduction in production costs (thanks to the significant increase in pot life), time savings (because no prior hydrolysis step) or even an improvement in the service life of the coatings in particular thanks to their better response to abrasion tests.

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• Chemical & Material Sciences (AREA)
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• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
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• Organic Chemistry (AREA)
• Paints Or Removers (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Polymerisation Methods In General (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

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• 2019
  • 2019-02-27 FR FR1902029A patent/FR3093013B1/fr active Active
• 2020
  • 2020-02-26 MX MX2021010332A patent/MX2021010332A/es unknown
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