WO2006097113A2 - Procede de production d'un dispositif optique, dispositif optique, et article comportant ledit dispositif optique - Google Patents

Procede de production d'un dispositif optique, dispositif optique, et article comportant ledit dispositif optique Download PDF

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Publication number
WO2006097113A2
WO2006097113A2 PCT/DK2006/050009 DK2006050009W WO2006097113A2 WO 2006097113 A2 WO2006097113 A2 WO 2006097113A2 DK 2006050009 W DK2006050009 W DK 2006050009W WO 2006097113 A2 WO2006097113 A2 WO 2006097113A2
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WIPO (PCT)
Prior art keywords
substrate
surface layer
elements
atoms
group
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PCT/DK2006/050009
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English (en)
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WO2006097113A3 (fr
Inventor
Maike Benter
Bahram Eshtehardi
Bjørn WINTHER-JENSEN
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Nanon A/S
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Publication of WO2006097113A2 publication Critical patent/WO2006097113A2/fr
Publication of WO2006097113A3 publication Critical patent/WO2006097113A3/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • 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
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • 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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/0006—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation
    • 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
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • 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
    • C03C2218/15—Deposition methods from the vapour phase

Definitions

  • the present invention relates to a method of producing an optical device, the optical device and an article comprising said optical device.
  • the invention in particular relates to a method of providing an optical device with a surface having anti-fog properties.
  • Condensing of water on surfaces of optical substrates is a well known problem or source of irritation.
  • a surface of a substrate has a temperature on or below the dew point of the air surrounding the substrate, water from the air will condense onto the surface often in the form of a blanket of very small droplets.
  • This blanket of small droplets is called 'fog' when the substrate is an optical substrate, as it often destroys or deteriorates the optical properties of the optical substrate.
  • Another and more general way of dealing with the problem has been to provide the optical device with an anti-fog coating to increase the energy of the surface, so that water fully wets to form a uniform film, with less interfering with light transmission or reflection.
  • EP 747460 discloses an anti-fog coating which can be used to provide glass and plastic with anti-fog properties.
  • This anti-fog coating is transparent and comprises a hydroxyl group containing polymer, an aluminium containing crosslinker, and a surface active agent containing hydroxyl and/or siloxane groups.
  • US 3726703 discloses a non-fogging coating comprising a highly cross-linked alkylene imine polymer.
  • US 6506446 discloses an anti-fog coating material containing a polyacrylic acid compound, polyvinyl alcohol and acetylacetone, and optionally sodium silicate.
  • US 5846650 describes an article comprising a substrate having a surface with a coating comprising a fluoropolymer and a fluorochemical surfactant.
  • the fluoropolymer and the fluorochemical surfactant are selected such that the article is anti-reflective, abrasion resistant and anti-fogging.
  • WO 9803575 discloses an anti-fog and scratch-resistant polyurethane composition which includes an isocyanate prepolymer, a hydrophilic polyol and an isocyanate- reactive surfactant.
  • US 5487920 discloses an anti-fog coating provided by a plasma deposition of polymerised silicon, which may further comprise the elements C, N and O. This anti-fog layer may be applied in a very thin layer.
  • the object of the present invention is to provide a novel anti-fog coating which can be used as an alternative to the prior art anti-fog coatings.
  • a further object of the invention is to provide an optical device with a novel anti-fog coating, which anti-fog coating has a high scratch resistance.
  • a further object of the invention is to provide an optical device with a novel anti-fog coating, which anti-fog coating has long durability.
  • a further object of the invention is to provide an optical device with a novel anti-fog coating, which anti-fog coating is easy to apply and need only be applied in a relatively thin layer.
  • a further object of the invention is to provide an optical device with a novel anti-fog coating, which anti-fog coating does not have any major effect upon the transparent and reflecting properties of the device.
  • a coating of an amorphous material comprising at least 5 % by atoms of the element P, at least 5 % by atoms of the element Si, and at least 0.2 % by weight of the elements selected from the group consisting of B, K, Li, Na, K, Mg, Ca, Ti, Fe, Cu, Ag, Zn, Al, Co, Ga, Zr, Y, Ni, Pb, Cd, In, Sn, Mn and mixtures thereof, wherein the elements P and Si are in oxidated form, can provide an optical substrate with very good anti-fog properties, which furthermore are long lasting and highly scratch resistant.
  • the amorphous material comprises in the range of 5.0-30% by atoms of the element P, such as between 10.0 and 25.0 % by atom, such as between 15.0 and 20.0 % by atom.
  • this coating of the invention can be applied in a very thin layer and also the method of applying the coating is very simple and cost effective.
  • the method of the invention of producing an optical device with a surface exhibiting anti-fog properties comprises the steps of providing an optical substrate; and applying a surface layer onto said substrate, said surface layer consisting of an amorphous material comprising at least 5 % by atoms of the element P, at least 5 % by atoms of the element Si, and at least 0.2 % by weight of the elements selected from the group consisting of B, K, Li, Na, K, Mg, Ca, Ti, Fe, Cu, Ag, Zn, Al, Co, Ga, Zr, Y, Ni, Pb, Cd, In, Sn, Mn and mixtures thereof, wherein the elements P and Si are in oxidated form.
  • the amorphous material may preferably comprise in the range of 5.0-30% by atoms of the element P, such as between 10.0 and 25.0 % by atom, such as between 15.0 and 20.0 % by atom.
  • the optical substrate may be any optical substrate, whether glass, plastic, etc., whether transparent, translucent, or reflecting, including, but not limited to automobile windows, mirrors of all types such as medical mirrors, dental mirrors, surgical mirrors, medical operating room equipment, instruments and gauges, microscopes, telescopes, camera lenses, prisms, picture coverings, microscope slides, reading glasses, sun glasses, lenses of all types, sport and skiing goggles, greenhouses, gas mask face plates, house windows, airplane windows, train and automobile windows, etc.
  • optical substrate in practise means a substrate where the optical properties have a purpose or a function in the final optical device.
  • the surface layer may comprises up to 30 % atom of one or more of the elements selected from the group consisting of Si, B, AL, Fe, and Ti, such as in the range of 2.0-20.0 % by atoms from the elements Si, B, AL, Fe, and Ti, such as at least 5 % by atoms from the elements Si, B, AL, Fe and Ti. It is preferred that at least some of the Si, B, AL, Fe and Ti atoms are present in the amorphous material. It is believed that the Si, B, AL, Fe and/or Ti elements in the above amounts provide the surface layer with increased scratch resistance in combination with the other elements.
  • the surface layer is essentially free of the element B.
  • the Si element in the surface layer may increase the scratch resistance.
  • the surface layer comprises up to 30 % atom of the element Si, such as in the range of 2.0-20.0 %, such as at least 5 % by atoms of the element Si.
  • the element Si may increase the scratch resistance of the surface layer, in particular if the Si element is bound in an oxide network with other elements.
  • the surface layer comprises up to about 50 % by atoms, such as up to about 40 % by atoms, such as between 0.2 and 30 % by atoms of one or more of the elements selected from the group consisting of Li, Na, K, Mg, Ca, Ti, Fe, Cu, Ag, Zn, Al, Co, Ga, Zr, Y, Ni, Pb, Cd, In, Sn and Mn.
  • the surface layer comprises in the range 30.0-80.0 % by atoms of the element O, such as between 45.0 and 70.0 % by atoms. It has thus been found that the optimal anti-fog properties can be obtained in the surface layer if fully oxidized.
  • these one or more element(s) are in the form of components which are partly or preferably fully oxidized.
  • At least some of the O atoms are chemically bonded to one or more of the atoms P, B, Si, K, Li, Na, K, Mg, Ca, Ti, Fe, Cu, Ag, Zn, Al, Co, Ga, Zr, Y, Ni, Pb, Cd, In, Sn and Mn.
  • the inorganic elements When the inorganic elements oxidize they may form an oxide network which is very strong and results in both high scratch resistance and long durability.
  • At least a part such as the major part by atoms of one or more of the elements selected from the group consisting of Li, Na, K, Mg, Ca, Ti, Fe, Cu, Ag, Zn, Al, Co, Ga, Zr, Y, Ni, Pb, Cd, In, Sn and Mn, is present in the form of an oxide network.
  • the surface layer comprises P and Si elements
  • the elements Si, and P and optionally other elements selected from the group consisting of B, Mg, Ca, Ti, Fe, Cu, Ag, Zn, Al, Co, Ga, Zr, Y, Ni, Pb, Cd, In, Sn and Mn are present in the form of an oxide network.
  • the oxide network may preferably comprise one or more elements selected from the group consisting of Na, K and Li in the mesh of the oxide network, e.g. under the influence of ionic forces, such as forming in an ion bonding with one of the elements of the oxide network.
  • the oxide network may preferably comprise alkali earth elements as cat ions to increase resistance towards hydrolyses, in particular if the optical device is adapted to be used in water.
  • the surface layer is preferably composed of the element P and one or more of the elements Si, K, Li, Na, K, Mg, Ca, Ti, Fe, Cu, Ag, Zn, Al, Co, Ga, Zr, Y, Ni, Pb, Cd, In, Sn and Mn, wherein the elements are in the form of an oxide network, optional Na, K and Li are present in the mesh of the network.
  • Oxide networks and the formation thereof in general are described in the handbook, Inorganic Polymers, by H. H. Ray, Academic Press, 1978, pages 54-90.
  • the surface layer may in one embodiment comprise a small amount of organic material, such as less than 6% by weight, preferably less than 4% by weight of organic compounds. However it is preferred that the surface layer is essentially free of organic compounds, i.e. the surface layer is essentially composed of inorganic components.
  • the substrate may be any kind of optical substrate.
  • the substrate is reflecting or transmitting at least 20 % by energy, such as at least 30 % such as at least 50 % by energy of electromagnetic waves.
  • the electromagnetic waves may preferably include radio waves (more than 30 cm, e.g. up to 3 km), microwave (0.3 -300 cm), infrared (0.7-300 ⁇ rm), visibly light (0.3-0.7 ⁇ m), ultraviolet (0.3 nm-0.3 ⁇ m), X-ray (0.03-3 nm), gamma (less than 0.03 nm).
  • the substrate is reflecting or transmitting at least 20 % by energy, such as at least 30 % such as at least 50 % by energy of visible light, preferably visible light having wavelengths in the range 400 to 700 nm, because the number of optical devices which are using the optical properties of the device in the visual area is very high,
  • optical devices include e.g. glasses, windows, car screens, instrument covers, goggles and others.
  • the substrate is reflecting or transmitting at least 20 % by energy, such as at least 30 % such as at least 50 % by energy of infrared light, preferably infrared light having wavelengths in the range 0.7 to 300 ⁇ m.
  • energy such as at least 30 % such as at least 50 % by energy of infrared light, preferably infrared light having wavelengths in the range 0.7 to 300 ⁇ m.
  • This property is particularly relevant to optical devices manipulating or operating with infrared light such as a bar code reader lens, a scanner lens, a telescope lens and similar.
  • the substrate may in one embodiment preferably have a refractive index above 1.4, such as between 1.5 and 2.2, such as between 1.55 and 1.8.
  • a refractive index above 1.4, such as between 1.5 and 2.2, such as between 1.55 and 1.8.
  • the refractive index is relatively high, as the lens thus may be relatively thin (and thereby light) and still provide a desired focussing or defocusing. For glasses this is a highly desired property.
  • the optical device may in principle be any type of device including optical glass or optical polymer devices.
  • Preferred devices include eyewear glasses; goggles and parts of goggles; optical lenses, such as telescope lenses, binocular lenses, microscope lenses, objective lenses, projection objective lenses, enlarging lenses, camera lenses, bar code reader lenses and scanner lenses; windows, such as cockpit windows (e.g. in a car, an air plain or other transport devices), show windows and showcases.
  • the optical device is a mirror or a screen, such as a lamp cover, a window (e.g. car window, air craft window), goggles, glasses, a medical device (e.g. a syringe and an ampoule), instrument covers (e.g. watch cover, thermometer cover) and a monitor screen (e.g. a pc screen, a mobile phone screen, a camera screen), a lens e.g. a lens of parabola, a microscope, a telescope, or a binocular.
  • the surface of the substrate onto which the surface layer is applied may have any shape, plane, curved, angular, edged, patterned or combinations.
  • the substrate has a curved surface, and the surface layer is applied onto this curved surface of the optical substrate.
  • the curved surface may e.g. be convex, concave or both.
  • the optical substrate may have any thickness, but in practice the optical substrate often has a thickness less than 20 cm or even less than 10 cm. In case the optical substrate is a transparent device, the thickness should preferably be even less. In one embodiment the optical substrate has a thickness up to about 10 cm, such as between 0.01 mm and 8 cm, such as between 0.1 and 20 mm.
  • the substrate may in one embodiment be of a transparent or semitransparent material, preferably in the form of a transparent or semitransparent glass, mineral glass and/or, polymer, such as a polymer selected from the group consisting of CR 39 (polydiethylene glycole bis allylcarbonate), Plexiglas (poly (methyl methacrylate), PE (polyethylene), PET (polyethylene terephatalate), PS (polystyrene), PC (polycarbonate), PP (polypropylene), PA (polyamide) or mixtures comprising one or more of these polymers.
  • CR 39 polydiethylene glycole bis allylcarbonate
  • Plexiglas poly (methyl methacrylate)
  • PE polyethylene
  • PET polyethylene terephatalate
  • PS polystyrene
  • PC polycarbonate
  • PP polypropylene
  • PA polyamide
  • the substrate is a transparent polymer. In another embodiment the substrate is a reflective material, such as a mirror.
  • the surface layer may preferably be relatively thin.
  • the thickness of the layer often depends on how it is applied. In general it is desired that the thickness is less than 100 ⁇ m. In one preferred embodiment the surface layer has a thickness of less than 2000 nm, preferably in the interval between 10 - 1000 nm, such as between 40 - 400 nm, such as up to 200 nm.
  • the surface layer may in principle be applied using any conventional method such as spraying, dipping, rolling, coating, printing, preferably followed by a post treatment including heating in the presence of oxygen, preferably to a temperature of at least 300 °C, such as above 500 °C, such as between 500 and 600 °C.
  • the element in the applied materials may preferably form an oxide network as disclosed above.
  • the post treatment may be performed as the post treatment disclosed below.
  • Preferred methods include plasma deposition, E-beam deposition and sol-gel application, preferably with a post treatment as disclosed herein.
  • sol-gel methods can be found in "Preparation of P 2 O 5 -SiO 2 glasses with proton conductivity of -100 mS/cm at room temperature", by M. Nogami et al.Journal of the Electrochemical Society, 151 (12) A2095-A2099 (2004). This method may be used by applying the hydrolyzed solution of the components in a thin layer onto the optical substrate, forming and solidifying the gels as described in the article.
  • E-beam coating methods in general are well known in the art, and further information about the general method can e.g. be found in "Coating Ophthalmic Lenses”. Cerac technical publication, Volume 7 - Issue 4, October - December, 1997 . Edited by Dr. Ervin Colton and in US6638857.
  • the surface layer is applied using plasma deposition.
  • plasma deposition By using plasma deposition a desired thin and even surface layer can be applied even when the substrate surface is curved, edged and uneven.
  • the method of applying the surface layer using plasma deposition is furthermore very fast, and cost effective since both time and the use of raw-material are minimised.
  • the method of the invention using plasma deposition includes the steps of placing the substrate in a reaction chamber and subjecting the substrate to a plasma deposition treatment for deposition of a plasma polymerized coating.
  • any plasma deposition methods may be used.
  • the plasma is generated by subjecting gas to an electric field generated by an electrode system comprising two or more electrodes connected to a power source.
  • the power source may in principle be any type of power source e.g.
  • AC alternating current
  • DC direct current
  • LF low frequency
  • AF audio frequency
  • RF radio frequency
  • microwave power source e.g. as described in EP 831 679 or WO 00/44207 which are hereby incorporated by reference.
  • the pressure in the deposition treatment step may preferably be 50 Pa or below, more preferably below 35 Pa, such as between 5 and 30 Pa, such as between 10 and 25 Pa, such as between 5 and 15 Pa.
  • the electric power can be supplied to the equipment at a high radio frequency, from about 40 KHz to 3 GHz, preferably from 13 to 27 MHz, and most conveniently at 13.56 MHz.
  • the electric power delivered to the apparatus can vary over a range of from about 2 to 10,600 watts. The power used is somewhat dependent on chamber working volume. The skilled person will be able to select an operable power for the plasma.
  • the deposition treatment comprises plasma treatment in the presence of a monomer gas.
  • the monomer gas is the source for the elements of the coating.
  • the gas may also comprise other components which are not deposited e.g. inert gasses.
  • the monomer gas comprises one or more of the compositions selected from the group consisting of organosilicon compositions, organophosphorous, organoborate, and/ or other organo metallic compounds such as Li, Na, Al and Ti; inorganic components such as inorganic hydrides, e.g.
  • the monomer gas comprises organosilicon such as hexamethyldisiloxane, methoxythmethylsilane, hexamethylcyclotrisiloxane, or phenylthethoxysilane.
  • the monomer gas comprises organophosphorous such as thmethylphosphite, trimethylphosphate, thethylphosphate, Di-i-propylphosphite, Diphenylphosphine, Dimethylphenylphosphine, Dimethylmethylphosphonate, diethylphsphite, th-n-propylphosphine.
  • organophosphorous such as thmethylphosphite, trimethylphosphate, thethylphosphate, Di-i-propylphosphite, Diphenylphosphine, Dimethylphenylphosphine, Dimethylmethylphosphonate, diethylphsphite, th-n-propylphosphine.
  • the monomer gas comprises organoborate and halogenated boron compounds such as trimethylborate, thethylborate, th-n-propylborate, ths(thmethylsilyl)borate, thethoxyboroxine, BX 3 and B 2 X 4 , wherein X means halogen selected from the group consisting of F, Cl and Br.
  • organoborate and halogenated boron compounds such as trimethylborate, thethylborate, th-n-propylborate, ths(thmethylsilyl)borate, thethoxyboroxine, BX 3 and B 2 X 4 , wherein X means halogen selected from the group consisting of F, Cl and Br.
  • the monomer gas comprises one or more of the components organo aluminium and halogenated aluminium compounds such as thmethylaluminium, thethylaluminium, ths(dimethylamido)aluminium aluminum t- butoxide, aluminum isopropoxide, aluminum acetylacetine and aluminiumtrichlohde.
  • organo aluminium and halogenated aluminium compounds such as thmethylaluminium, thethylaluminium, ths(dimethylamido)aluminium aluminum t- butoxide, aluminum isopropoxide, aluminum acetylacetine and aluminiumtrichlohde.
  • the monomer gas comprises one or more of the hydrides, AIH 3 , PH 3 , P 2 H 4 , P 3 H 5 , BH 3 , B 2 H 6 , B 4 H 10 , B 5 H 9 ,and SiH 4 , Si 2 H 6 , Si 3 H 8 .
  • the monomer gas may preferably be fed into the reaction chamber together with a support gas selected from the group consisting of inert gases and oxidizing gasses, the support gas preferably being selected from the group consisting of N 2 O, Ar, O 2 and mixtures thereof.
  • a support gas may provide a good distribution of the monomer gas and furthermore the oxygen may further oxidize the elements of the surface layer.
  • the skilled person will by a few experiments be able to find an optimal amount of the monomer gas. Often it is desired that the monomer gas is fed into the reaction chamber in an amount of between 0.1 and 100 ml/min as determined at 25 °C and 1 atm.
  • the feeding may be stepwise or continuous over the treatment time.
  • the deposition step is performed for at least 1 minute, such as at least 5 minutes, such as between 5 and 120 minutes, such as between 10 and 60 minutes.
  • the plasma deposition may comprise a step of pre-treating the surface of the substrate. This pre-treating step is performed prior to the deposition step. It need not be performed immediately prior to the plasma deposition step, but in general it is preferred that it is performed within 24 hours, more preferably within 5 hours, more preferably within 2 hours before the plasma deposition. Often it is most simple to perform the pre-treatment step immediately prior to the plasma deposition step.
  • the pre-treatment step is in particular useful if the optical substrate is of or comprises glass.
  • the pre-treatment step preferably comprises the step of subjecting the substrate surface to an oxidising gas.
  • the oxidizing gas in the pre-treatment step may preferably comprise one or more oxidising components selected from the group consisting of O 2 , N 2 O and mixtures thereof.
  • the oxidizing gas comprises one or more oxidizing components in combination with one or more inert gasses selected from the group consisting of argon helium neon and krypton.
  • the oxidizing gas comprises a mixture of O 2 and argon.
  • the pre-treatment step may preferably be performed in a plasma, e.g. generated by any of the power sources as disclosed above.
  • the pressure in the pre- treatment plasma may preferably be 50 Pa or below, below 35 Pa, such as between 10 and 30 Pa, such as between 10 and 15 Pa.
  • the method of the invention using plasma deposition further 5 comprises a step of activating the surface of the substrate.
  • the activating step is performed prior to the deposition step and preferably prior to the pre-treatment step, if any.
  • the activating step may be used on any type of surface, but it is in particular 10 effective on polymer based surfaces.
  • the activation step can make the surface more reactive towards the monomer gases in the plasma, and thus provide a faster and more adhering deposition.
  • the activation step preferably includes the step of activating the surface by 15 subjecting it to a reducing gas under reduced pressure, e.g. performed in a plasma.
  • the activating step is performed in a plasma and the pressure in the activating step is 50 Pa or below, preferably below 35 Pa, such as between 20 10 and 30 Pa, such as between 10 and 15 Pa.
  • the reducing gas used in the activating step may preferably comprise one or more reducing components selected from the group consisting of H 2 , hydrocarbons (such as hexene), acetylene, oxygen, and mixtures thereof.
  • the reducing gas comprises one or more reducing components in combination with one or more inert gasses selected from the group consisting of argon, helium, neon, or krypton.
  • the reducing gas used in the activating step comprises a 30 mixture of H 2 and argon, or a mixture of H 2 , argon and a hydrocarbon.
  • the activation step may be performed in one or more sub steps.
  • the activating step is performed in two or more sub steps including a first activating sub step using H 2 and argon and a second activation sub step using H 2 , argon and a hydrocarbon.
  • a very good activation may be obtained in the activating step wherein the reducing gas comprises a mixture of H 2 and argon, or a mixture of H 2 , argon and a hydrocarbon, argon and a hydrocarbon, or argon and acetylene, and preferably the activating step is performed in one or more sub steps including a first activating sub step using argon and a second activation sub step using a hydrocarbon or acetylene and argon.
  • the pressure in at least one sub step of the activating step is 25 Pa or below, preferably below 20 Pa, such as between 0.1 and 18 Pa, such as between 5 and 15 Pa, preferably in the interval between 9 and 12 Pa.
  • the method of the invention using plasma deposition further comprises a post treatment step of post treating the surface of the substrate, said post treatment step being performed after termination of the deposition step.
  • the post treatment step may preferably include treatment with an oxidizing component in a plasma, the oxidizing component preferably being oxygen.
  • the post treatment step includes subjecting the substrate to raised temperature, such as a temperature above 100 °C, such as above 200 °C, such as above 500 °C, such as between 500 and 600 °C.
  • raised temperature such as a temperature above 100 °C, such as above 200 °C, such as above 500 °C, such as between 500 and 600 °C.
  • the substrate may e.g. be in an oxygen containing reactor.
  • the heat treatment may decompose organic material in the surface layer, and it may further result in that the elements in the layer are arranged in a oxide network.
  • the post treatment step may in one embodiment include subjecting the substrate to a treatment with water optionally in combination with oxygen.
  • the post treatment step may be performed for e.g. 1 minute to weeks, but in practice the post treatment may preferably be performed for least 15 minutes, preferably between 0.5 and 24 hours, such as between 1 and 12 hours, such as between 2 and 6 hours.
  • An embodiment of the method of the invention wherein the optical substrate is of glass, and which has proved to give a surface with a very high anti-fog quality and a high scratch resistance comprises the steps of i) placing the substrate in a reaction chamber ii) activating the surface by subjecting it to a reducing gas under reduced pressure, iii) pre-treating the surface by subjecting it to an oxidizing gas, and iv) subjecting the substrate to a plasma deposition treatment for deposition of a plasma polymerized coating.
  • the activating step comprises activating the surface in a plasma using one or more of the compositions selected from the group consisting of H 2 , NH 3 , B 2 H 4 , F 2 and hydrocarbons optionally in combination with one or more inert gasses such as argon.
  • the hydrocarbons may preferably be selected from the group consisting of alkanes Ci - Ci 5 , alkenes C 2 - Ci 5 , alkynes C 2 - Ci 5 , and styrene, aromatic monomers of styrene compounds, monomers of vinyl- and acrylate- compounds.
  • the one or more compositions used in the activation step are a mixture of H 2 and argon.
  • the method comprises the steps of a) placing the substrate in a reaction chamber b) pre-treating the surface by subjecting it to an oxidizing gas, and c) subjecting the substrate to a plasma deposition treatment for deposition of a plasma polymerized coating.
  • the method may preferably comprise the following steps of plasma polymerization:
  • a mixture contains an organophosphorous and organoborate compound. • a mixture contains an organophosphorous, organoborate and silanes compound, and
  • a mixture contains an organophosphorous, organoborate, silanes, and/ or - other oregano metallic compounds such as oregano metallic compounds comprising Li, Na, Al and Ti.
  • the invention also relates to a device, in particular an optical device with an anti- fog surface obtainable by the method of the invention.
  • the optical device with an anti-fog surface comprises a surface layer of a material comprising surface layer consisting of an amorphous material comprising in the range of 5.0-30% by atoms of the element P, such as between 10.0 and 25.0 % by atom, such as between 15.0 and 20.0 % by atom, and the element P is present in the form of an oxide network.
  • the surface layer may preferably comprise Si and optionally one or more of the elements B, AL, Fe, and Ti, so that the total amount of Si, B, AL, Fe and Ti preferably is between 2.0 and 20 % by atoms, such as at least 5 % by atoms.
  • the elements P, Si and optionally B, AL, Fe and Ti are present in the form of an oxide network.
  • the surface layer comprises P and Si elements and optionally other elements selected from the group consisting of B, Mg, Ca, Ti, Fe, Cu, Ag, Zn, Al, Co, Ga, Zr, Y, Ni, Pb, Cd, In, Sn and Mn.
  • These elements are present in the form of an oxide network, and optionally one or more elements selected from the group consisting of Na, K and Li are present in the mesh of the oxide network, e.g. under the influence of ionic forces, such as forming an ion bonding with one of the elements of the oxide network.
  • the surface layer may preferably have a thickness of less than 2000 nm, preferably in the interval between 10 - 1000 nm, such as between 40 - 400 nm, such as up to 200 nm.
  • the surface layer may preferably have a scratch resistance which is at least as high as the scratch resistance of the substrate prior to coating.
  • Untreated PE substrates and glass substrates for goggles were used as substrate samples.
  • the pre-treatment step was made to clean and activate the surface of the samples.
  • the pre-treatment was performed in a plasma.
  • the plasma chamber had a volume of 12.1 L (3 phase AC plasma, with a max current and voltage at 20OmA and 650V on 50 Hz). Table 1 below shows the parameters and conditions.
  • Results and discussion The samples were investigated by FTIR. The investigation was made immediately after the treatment and was repeated a day after the treatment. The samples were washed with water and a spectrum was made before and after washing.
  • Test 1 The deposition of Test 1 on both the PE and the glass sample made by TMP was almost gone by washing, in tests 2 - 4 where TMP also had been used the peaks connected to P-O were still there after washing. This means that there must exist a net which has a chemical composition of P, O, and Si. The solubility of existing glass from test 2 to 4 decreases by increasing of HMDS.
  • Treatment As in example 1 and as shown in table 5.
  • the test included both the PE samples and glass samples.
  • Plasma chamber approx 15 litter
  • Electrodes cylindrical stainless metal sheet (approx. 1 150 cm 2 surface area) and cylindrical net (approximately 900 cm 2 surface area).
  • Activation / pre-treatment The samples were placed in the plasma chamber. A hydrogen flow rate at 6.1 ml/min stabilized the pressure on 1 1 Pa. The samples were pre-treated for 3 minutes with a power at 96 W (0.67 kV).
  • Treatment After 3 minutes activation, the treatment was started with feeding of 2.2 ml/min of HMDSO (hexamethyldisiloxane) followed by Ar/oxygen (12 ml/min): The hydrogen flow was stopped and after a few seconds the Ar/oxygen flow was changed to oxygen. After one minute of treating, feeding with TMP (trimethylphosphite) on 2.3 ml/min was started. During 1 minute the TMP flow rate was increased to 4.2 ml/min. The pressure was stabilized on approximately 22 Pa. The treatment took about 15 minutes with a power of 97 W (0.6 kV). After 15 min. of treatment, feeding of the monomers was terminated. Examination using FTIR shows good peaks which indicated P-O and Si-O bonding. The deposition behaves hydrophilic and stable.
  • HMDSO hexamethyldisiloxane
  • Ar/oxygen (12 ml/min)
  • the test included both the PE samples and glass samples.
  • Electrodes cylindrical stainless metal sheet (approx. 1 150 cm2 surface area) and disk (approx. 143 cm2 surface area). The disk placed in the bottom of cylindrical electrode perpendicular to each other.
  • Activation / pre-treatment The samples were placed in the plasma chamber. A hydrogen flow rate at 5.0 ml/min stabilized the pressure at 10 Pa. The samples were treated for 3 minutes with a power of 1 10 W (0.47 kV).
  • Treatment After 3 min activation, the treatment was initiated with feeding of HMDSO (hexamethyldisiloxane) in an amount of about 1.5 ml/min followed by termination of the hydrogen flow and turning on oxygen feeding (1 1.6 ml/min). After one minute feeding with TMP (thmethylphosphite) on 2.3 ml/min and TMB (trimethylborate) on 0.5 ml/min was started. During 20 seconds the TMP flow was increased to 3.4 ml/min. The pressure was stabilized on approx. 27 Pa. The treatment took about 4 minutes with a power of 190 W (0.275 kV). After 4 min treatment the feeding with monomers was terminated. The oxygen feeding was continued for two minutes.
  • HMDSO hexamethyldisiloxane
  • the final coating has a thickness abut 100 nm. Examination using FTIR shows peaks which indicated P-O, P-O-P, Si-O-Si and Si-O bonding, very small peak at approx 1725 cm "1 connected to C-O. The deposition behaves hydrophilic and stable.
  • TMOS Tetramethoxysilane
  • TMP Thmethylphosphite
  • TMAI Trimethylaluminum
  • Substrater glas (1 ), PE (2), Aluminium oxide (Mineral glass)(3), PET (4), PC, PC lens (5), glas lens (6).
  • Step 2b The Ar flow was stopped and O2 introduced at 8 ml/min.
  • Step 2 O2 was introduced (27 ml/min), and H2 flow adjusted to 6 ml/min.
  • TMP 1 ,3 ml/min
  • TMAI 1 ,1 ml/min
  • the treatment time was 7 min.

Abstract

La présente invention a trait à un procédé de production d'un dispositif optique avec une surface présentant des propriétés antibuée. Le procédé comprend les étapes suivantes: la mise à disposition d'un substrat optique; et l'application d'une couche superficielle sur ledit substrat, la couche superficielle étant constituée d'un matériau amorphe comprenant au moins 5% en atomes de l'élément P, au moins 5% en atomes de l'élément Si, et au moins 0,2% en poids des éléments choisis parmi le groupe constitué de B, K, Li, Na, K, Mg, Ca, Ti, Fe, Cu, Ag, Zn, Al, Co, Ga, Zr, Y, Ni, Pb, Cd, In, Sn, Mn et des mélanges de ceux-ci, lesdits éléments P et Si étant sous forme oxydée. Le substrat optique présente un résistance à la rayure et le revêtement antibuée présente une longue durabilité. L'invention a également trait à un dispositif optique avec une surface antibuée susceptible d'être obtenu par le procédé de l'invention. Le dispositif optique peut être, par exemple, un miroir ou un écran, un abat-jour, une fenêtre (par exemple, une vitre de véhicule automobile, ou un hublot d'aéronef), des lunettes de protection, des verres, un dispositif médical (par exemple, une seringue et une ampoule), des boîtiers d'instruments (par exemple, un boîtier de montre, un boîtier de thermomètre) et un écran de moniteur (par exemple, un écran d'ordinateur personnel, un écran de téléphone mobile, un écran de caméra), une lentille, par exemple, une lentille de parabole, d'un microscope, d'un télescope ou de jumelles.
PCT/DK2006/050009 2005-03-18 2006-03-20 Procede de production d'un dispositif optique, dispositif optique, et article comportant ledit dispositif optique WO2006097113A2 (fr)

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Publication number Priority date Publication date Assignee Title
WO2010141594A1 (fr) * 2009-06-02 2010-12-09 Massachusetts Institute Of Technology Revêtements
CN103003374A (zh) * 2010-07-30 2013-03-27 埃西勒国际通用光学公司 制备具有防雾层层组装涂层的制品的方法和具有改进的防雾和耐久性的涂覆制品
CN104219431A (zh) * 2014-09-12 2014-12-17 宁波中研瑞华数字技术有限公司 一种户外防雾全景摄像机
US11066745B2 (en) * 2014-03-28 2021-07-20 Sio2 Medical Products, Inc. Antistatic coatings for plastic vessels
CN117567042A (zh) * 2023-11-18 2024-02-20 东莞市晟鼎精密仪器有限公司 一种用于镜片防雾的微波等离子处理工艺

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EP0887179A1 (fr) * 1996-12-09 1998-12-30 Nippon Sheet Glass Co., Ltd. Article anti-buee et son procede de production
JPH11172148A (ja) * 1997-12-12 1999-06-29 Kobe Steel Ltd 親水性塗料及び親水性基材の製造方法
EP1336592A1 (fr) * 2002-02-12 2003-08-20 Canon Kabushiki Kaisha Composition de revêtement anti-buée, couche de revêtement anti-buée et élément optique anti-buée

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Publication number Priority date Publication date Assignee Title
EP0887179A1 (fr) * 1996-12-09 1998-12-30 Nippon Sheet Glass Co., Ltd. Article anti-buee et son procede de production
JPH11172148A (ja) * 1997-12-12 1999-06-29 Kobe Steel Ltd 親水性塗料及び親水性基材の製造方法
EP1336592A1 (fr) * 2002-02-12 2003-08-20 Canon Kabushiki Kaisha Composition de revêtement anti-buée, couche de revêtement anti-buée et élément optique anti-buée

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010141594A1 (fr) * 2009-06-02 2010-12-09 Massachusetts Institute Of Technology Revêtements
US8986848B2 (en) 2009-06-02 2015-03-24 Massachusetts Institute Of Technology Coatings
CN103003374A (zh) * 2010-07-30 2013-03-27 埃西勒国际通用光学公司 制备具有防雾层层组装涂层的制品的方法和具有改进的防雾和耐久性的涂覆制品
CN103003374B (zh) * 2010-07-30 2016-03-02 埃西勒国际通用光学公司 制备具有防雾层层组装涂层的制品的方法和具有改进的防雾和耐久性的涂覆制品
US11066745B2 (en) * 2014-03-28 2021-07-20 Sio2 Medical Products, Inc. Antistatic coatings for plastic vessels
US20210363631A1 (en) * 2014-03-28 2021-11-25 Sio2 Medical Products, Inc. Antistatic coatings for plastic vessels
CN104219431A (zh) * 2014-09-12 2014-12-17 宁波中研瑞华数字技术有限公司 一种户外防雾全景摄像机
CN117567042A (zh) * 2023-11-18 2024-02-20 东莞市晟鼎精密仪器有限公司 一种用于镜片防雾的微波等离子处理工艺

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