WO2012020295A1 - Eléments optiques ayant des propriétés hydrophiles et antibuée de longue durée et leur procédé de préparation - Google Patents

Eléments optiques ayant des propriétés hydrophiles et antibuée de longue durée et leur procédé de préparation Download PDF

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Publication number
WO2012020295A1
WO2012020295A1 PCT/IB2011/001791 IB2011001791W WO2012020295A1 WO 2012020295 A1 WO2012020295 A1 WO 2012020295A1 IB 2011001791 W IB2011001791 W IB 2011001791W WO 2012020295 A1 WO2012020295 A1 WO 2012020295A1
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Prior art keywords
film
less
hydrophilic
optical element
range
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PCT/IB2011/001791
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English (en)
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WO2012020295A8 (fr
Inventor
Rosa Di Mundo
Fabio Palumbo
Riccardo D'agostino
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6/6Università Degli Studi Di Bari
Plasma Solution S.R.L.
Consiglio Nazionale Delle Ricerche (10%)
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Publication of WO2012020295A1 publication Critical patent/WO2012020295A1/fr
Publication of WO2012020295A8 publication Critical patent/WO2012020295A8/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • 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

Definitions

  • This invention relates to new plastic optical elements having permanent hydrophilic and anti-fog properties and to a method for their production. More in particular the invention concerns transparent plastic elements such as optical elements, but not exclusively, whose surface is treated to provide the same with hydrophilic and, therefore, anti-fog properties, and preferably also anti- reflective properties, that are stable and permanent in time.
  • hydrophilic we want to define also the wording superhydrophilic and to define surfaces having properties corresponding to ACA angles within the range of 30° to 0° (zero degrees) as better explained hereinafter.
  • transparent plastic material such as ophthalmic lenses, protective shields and visors, swimming goggles, ski masks, windows / showcases in plastic material, walls of refrigerated counters, windshield
  • transparent plastic material is intended to be made from plastic polymers such as e.g. polycarbonate, polymethylmethacrylate and polyolefins such as polyethylene terephthalate, polyethylene naphthalate, polystyrene, polyethylene, polypropylene or similar.
  • the fogging develops when the steam condenses on a surface not-sufficiently hydrophilic, i.e. a set of micro-droplets with a rounded shape is deposited on the surface, causing internal reflections in the light transmitted through the polymer material (see Figure 1 ).
  • Another problem with such optical components is the reflection of light on their surface reducing light transmission and producing unwanted glare.
  • One method (which includes products such as Visgard ®, Vistex ®) consists in covering the surface of interest with a transparent film (typically polyethylene terephthalate, PET) with a thickness of about 100 ⁇ layer, provided with an hydrophilic polymer top.
  • a transparent film typically polyethylene terephthalate, PET
  • Another very common method consists in using chemical mixtures to be periodically applied on the surface of the optical component. If the object is small, it is dipped in the product. Alternatively, these products are applied as paints (eg. Chamelic). Examples of solutions of the type above described are shown in the following documents.
  • JP2005029723 uses a mixture of two components (isocyanate/polyols and surfactants).
  • EP0399441 (1990) describes a mixture of hydrophilic monomer (polyethylene glycol dimethacrylate) and surfactant.
  • US5804612 (1998) refers to a polymer containing a hydroxyl group, a cross- linker containing aluminum, and a surface agent containing hydroxyl and/or siloxane groups.
  • US 2010/0033819 (2010) provides the deposit on the optical material to be treated of a hydrophilic polymer with conventional methods and a subsequent treatment with plasma etching of the hydrophilic polymer layer to ultimately achieve an anti-fog effect and a simultaneous anti-reflecting effect.
  • the process described in that patent is complex and long to achieve, consisting in a number of steps with different technologies and reactors.
  • the planned steps are: the deposition of a hydrophilic polymer layer (unclear technique, however, not based on plasma chemistry); deposition with another technique of a thin film of titanium dioxide as a catalyst for etching, etching with a plasma chemistry technique for nanostructuring; deposition with additional layers to improve the mechanical properties of the surface.
  • the invention also concerns a method according to claim 9; said plasmochemical method for treating the surface of the optical elements includes the steps of (i) nanostructuring (forming a nanostructure on) the surface of the optical elements using plasma etching and (ii) subsequent deposition of transparent hydrophilic film SiO x on the nanostructured surface. According to a preferred aspect of the invention, these steps are performed sequentially in the same reactor. Alternatively, they are carried out in different reactors.
  • This method gives the surface stable superhydrophilic character (with wetting in permeation regime) showing anti-fogging property.
  • the superhydrophilic characteristic of the surface that has been treated according to the present invention can be used for other purposes in addition to the antifogging use.
  • the method consists of a first step for directly nano-structuring the optical element surface by means of plasma etching, and a second step for coating the nano-structured surface with a transparent hydrophilic film that is stable in water and only a few nanometers thick.
  • the nano-structuring is directly made on the body of the optical element, in absence of films or layers deposited on it, and it does not alter the transparency of the polymer because the average distance and width of the nano-structures do not exceed the wavelength of visible spectrum, i.e. the nano-structures obtained according to the invention have width and distance dimensions between them smaller than 400 nm.
  • the material of the optical component to be treated is a transparent plastic material suitable for said use, such as for example polycarbonate (PC), polymethylmethacrylate (PMMA) and polyolefins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polystyrene (PS), polyethylene ( PE), polypropylene (PP) or similar.
  • PC polycarbonate
  • PMMA polymethylmethacrylate
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PS polystyrene
  • PE polyethylene
  • PE polypropylene
  • the processing of plasma etching extends into the surface of the component material to a depth from 50 nm to 1000 nm, preferably between 100 nm and 600 nm, more preferably between 200 nm and 400 nm and even more preferably between 300 nm and 400 nm.
  • the plasma etching processing is performed in a low pressure capacitive coupling plasma reactor.
  • the plasma is fed with oxygen or fluorocarbon gas or mixtures thereof, but preferably only oxygen at a flow rate in the range from 5 to 100 seem (standard cubic centimeters per minute), the pressure is in the range 30-200 mTorr, and preferably between 50 and 100 mTorr with a power approximately in the range 0.1 -1 W/cm 3 , for a time within the range 5-20 min.
  • the second method step which is the deposition of a hydrophilic film on the surface provided with the aforementioned nano-structures, is performed in the same reactor in which the first step of plasma etching or nano-structuring of the optical element body is carried out.
  • the hydrophilic film has a thickness in the range of 10 nm and 50 nm.
  • This film is preferably inorganic, e.g. composed of silicon oxide, SiOx with stoichiometric ratio x between 1.5 and 2.0, preferably within 1.7 and 2.0 and most preferably as close as possible to 2.
  • the material of the film can be defined by its contact angle with water (WCA) and is such that when the material is deposited as a film on a smooth flat surface (e.g. glass or crystalline silicon) its contact angle with water is less than 50°, preferably equal to or less than 35° and more preferably less than or equal to 15°.
  • the film that is deposited on the nanostructure with the above mentioned thickness is composed of silica oxide SiOx having stoichiometric x ratio within the range of 1.7 to 2.0, where the content of Carbon is originated substantially only from surface contamination and not from C-Si bonding; i.e. the C is present on the surface in the absence of C-Si bonds (no C-Si bonds are present).
  • the presence or absence of C-Si bonds can be detected with an XPS (X-ray photoelectron spectroscopy) analysis, with monochromatic source, by examining the photoelectronic peaks relevant to silica. These peaks should confirm the presence only of bonds Si(- 0) 3- 4 , e.g. a signal Si2p symmetrical that falls at 103.5 eV (+_0.2) having a width at half of its height that is 1.8-2.2 eV.
  • materials suitable to form an anti-fogging film are materials that are inert in water and that can be deposited as thin films conforming to the nano- structured surface.
  • the relevant Water Contact Angle on a film of said material deposited on a smooth surface is less than 50°, preferably less than 35° and most preferably less than 15°.
  • hydrophilic film as defined above presents (on a smooth surface) a contact angle below 50 ° a significant anti-fog effect is obtained and that this effect is stable over time, until at least 12 months, if the contact angle is equal to or less than 35 °.
  • a contact angle less than 15 ° allows for long life of the desired properties even when the height of the nanostructures is relatively low, for example, between 80 and 200 nm.
  • the deposition of SiOx thin film with x « 2 is carried out in a low pressure plasma reactor with capacitive coupling, feeding the plasma with generic organosilanes precursor, but preferably hexamethyldisiloxane (HMDSO) in mixtures with oxygen or mixed with oxygen and argon.
  • HMDSO hexamethyldisiloxane
  • the ratio of oxygen to organosilane is in the range between 25 and 50 (seem / seem) at a total flow rate between 100 and 200 seem, pressure between 70 and 200 mTorr and power density in the range of 0.4 and 1 W/cm3.
  • the time length of the process in the reactor is chosen in order to obtain a thickness in the range 10-50 nm, and usually ranges from 20 s to few min (e.g. 6-8 min).
  • Preferred embodiments are those in which the above discussed contact angle (WCA) is equal to or less than 35 0 with a height of nanostructures at least of 200 nm and width and distance below 400 nm. Also preferred embodiments are those wherein the said contact angle (WCA) is equal to or less than 15 ° with a height of nanostructures at least of 100 nm, width and distance below 400 nm. Finally, preferential embodiments are those with the above defined contact angle of the film that is equal to or less than 15 °, height of nano-structures that is at least 300 nm and width and distance that is less than 400 nm.
  • the invention has several advantages over the prior art.
  • Another important advantage of this invention is that the highly hydrophilic thin film characteristics (contact angle on smooth flat surface that is less than 35 °, but preferably less than 15 °) and the presence of the previously described nano-structures mean that the water-solid contact on these surfaces comes in a permeation regime, i.e. that a thin liquid film is formed, extending over the surface (see fig. 3).
  • This liquid film results in a maximum anti-fog effect (light transmission is not reduced at all) and because of the extended surface, the extended liquid film quickly evaporates.
  • the surface treated according to the invention has an angle ACA measured according to standard ASTM D7334-08, that is equal or less than 30°, preferably less than 10° and most preferably within the range of 0° to 6°; this surface has an exceptional antifogging behaviour.
  • the anti-fog behavior of these surfaces is stable over time; it was experimentally verified that the treated material according to the invention maintains the same performance for more than four months and surely for at least 12 months.
  • the film Because of the inorganic nature of the thin film deposited on nanostructures, the film provides a mechanical strength greater than or equal to that of the pristine polymer/optical element.
  • the nano-structuring process by plasma etching allows to reduce reflection of light on the surface, and thus increase the transmission (moth-eye effect).
  • This effect occurs when (i) nano-structures have width and average distance such that, as reported above, scattering is avoided and transparency is ensured (i.e., having size and distance between them less than the wavelength of visible light, 400 nm) and (ii) a height exceeding 100 nm but preferably above 200 nm.
  • FIG. 1-4 is a diagram that illustrates the different wetting and visibility of a treated surface (Fig. 3 and 4) with respect to the same untreated surface (Fig. 1 and 2);
  • FIG. 5 is a diagram showing a manufacturing process of a surface in accordance with the present invention.
  • FIG. 6 is a diagram of reactor suitable to carry out the process of the present invention.
  • - Fig. 7 and 8 are photographs showing the different behavior of the same material without and with surface treatment according to the invention
  • - Fig. 9 is a graph showing the behavior in time of a surface treated according to this invention with respect to known surfaces.
  • Figs. 1 and 2 it is shown warm moist air condensing on a transparent cold surface 1 , that was not treated according to the invention; condensation causes fogging by depositing on the surface a set of micro-drops 2 with round shape that causes internal reflections of the light transmitted through the polymer material (see Figure 2).
  • Fig. 3 and 4 show the different arrangement of condensed water on a surface 3 treated with the method according to the invention: in this case instead of a drop a liquid film 4 is formed, that does not alter the light transmission (Fig. 4 ).
  • the process according to the invention provides to initially submit (step A in Fig. 5) at least one surface 5 of a transparent plastic material 6 to a plasma etching treatment to obtain a nanostructured surface 5.
  • the plastic is of the type suitable for use in a component or in an optical element such as, for example, polycarbonate (PC), polymethyl methacrylate (PMMA) and polyolefins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polystyrene (PS) Polyethylene (PE), polypropylene (PP) or similar.
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PS polystyrene
  • PE Polyethylene
  • PP polypropylene
  • the plasma etching processing is carried out in a way known in the art, for example as described in "R. Di Mundo, F. Palumbo, R. d'Agostino, Nanostructuring of polystyrene in fluorocarbon plasmas: from sticky to slippery supemydrophobicity, Langmuir, 24, 5044-5051, (2008) possibly modified as per the following details.
  • the treatment involves the following operative parameters.
  • the treatment by plasma etching is carried out in a stainless steel plasma reactor 7, at low pressure and with capacitive coupling; the rector is provided in a known manner with an upper electrode 14 and a lower electrode 15 and vacuum means such as rotary pump 8 and turbo molecular pump 9. There can be one pump, only.
  • the electrode 14 is connected to the ground and electrode 15 is powered with RF.
  • the pressure in the reactor is controlled with a pressure transducer 10 and the plasma is fed with oxygen or fluorocarbon gas or mixtures thereof coming from the corresponding sources of gas through flow rate regulators 11 and 12; preferably, only oxygen is fed to the reactor.
  • the gas, or the gas mixture is fed to a ring nozzle 13 positioned near top electrode 14.
  • the flow rate is preferably within the range of 5 to 100 seem (standard cubic centimeters per minute), at a pressure within the range 30-200 mTorr, preferably in the range 50-100 mTorr, with a power density within the range 0.1 -1 W/cm 3 , for a time within the range 5-20 min.
  • the cm 3 used to define the power density refer to the volume between the two electrodes, 13 e 14, in the reactor, as the power supplied is divided by the volume of the space between the two electrodes.
  • This process allows to provide a proper nano-structure on plastic materials directly on the surface of the body, even without the step of pre-depositing an initial layer, which step is required by previous techniques.
  • the plasma etching processing leads to a roughening of the surface due to its nanostructuring, i.e. a physical change at nanometers level of surface 5, on which depressions are created and the treatment is controlled to obtain a modification of the surface through a series of nano-structures in the form of depressions 7 (separated by corresponding reliefs) that extend into the surface of the material to a depth of at least 50 nm and typically in the range between 50 nm and 1000 nm.
  • Such depth which corresponds to the height of the depressions, i.e. of the nano structures 7, is preferably between 100 nm and 600 nm, more preferably between 200 and 400 nm and even more preferably between 300 and 400 nm.
  • the average width L and the average distance D between the nano-structures (or depressions) 7 is less than 400 nm and preferably is in the range between 50 nm and 400 nm.
  • the following step provides to deposit a thin layer, or film, 15 of a hydrophilic material on the nano-structured surface 5; this step, too, is done with a plasma process.
  • the thickness of the deposited film 15 is preferably within the range of 10 nm to 50 nm.
  • Materials suitable for the deposition on the nano-structures 7 are preferably inorganic and they are anyway those who are able to provide, when deposited with the same method and with the same thickness on a flat, smooth surface (e.g. glass or crystalline silicon) a thin layer or film that has such a contact angle (WCA, water contact angle measured as ACA - advancing contact angle) with a drop of water that is less than 50°, preferably less than or equal to 35° and more preferably less than or equal to 15 degrees.
  • WCA water contact angle measured as ACA - advancing contact angle
  • the contact angle is measured as "advancing" (ACA) contact angle in accordance with ASTM D7334-08, i.e. by using drops of distilled water with a volume between 1 and 20 ⁇ , preferably between 1 ⁇ and 5 ⁇ , and measuring the angle as soon as the droplet comes in contact with the surface. Further details on the procedure for the evaluation of the contact angle are shown in the experimental part of the aforementioned paper by Mundo et al., Langmuir, 24, 5044-5051 , (2008).
  • the hydrophilic film is preferably inorganic.
  • a preferred film is composed of silicon oxide, SiO x with stoichiometric ratio x between 1.5 and 2.0, preferably 1.7 to 2; other materials that can also be suitable are those inert in water, that can be deposited in the form of thin films following the nano-structured surface.
  • the coatings that can be used are those which, when deposited under the same conditions (i.e. with the same method of the invention) on a flat, smooth surface such as glass or crystalline silicon, are able to provide a contact angle with distilled water (measured in accordance with the above mentioned standard) that is lower than 50 °, preferably less than or equal to 35 ° and more preferably less than or equal to 15 °.
  • the deposition of SiOx thin films with x within the range 1.7-2.0 and preferably about 2.0 is done in the low pressure plasma reactor, with capacitive coupling, shown in fig. 6, provided for this purpose with a source of organosilanes (HMDSO) and a source of argon (Ar).
  • HMDSO organosilanes
  • Ar argon
  • a film as defined above is substantially free of carbon CHx groups arising from the organosilane used in plasma deposition process.
  • a film as above defined is substantially free from carbon groups CHx deriving from the organosilanic compound used in the deposition plasma process.
  • SiOx films are preferred where the superficial (surface) content of Carbon as detectable with an XPS (X-ray photoelectron spectroscopy) analysis, with monochromatic source, is only deriving from surface contamination. This corresponds to photoelectronic peaks relevant to silica that show the presence only of bonds Si(-O)3-4 (e.g. a signal Si2p symmetrical that falls at 103.5 eV ( ⁇ 0.2) having a width at half of its height that is 1.8-2.2 eV). Such a film of silica oxide is able to provide the best performances.
  • the plasma is in fact supplied by an organosilane precursor, preferably hexamethyldisiloxane (HMDSO) in mixtures with oxygen or mixed with oxygen and argon, with a ratio of oxygen to organosilane in the range between 25 and 50 (seem / seem) at a rate of total flow between 100 and 200 seem; at a pressure between 70 and 200 mTorr and with a power density in the range of 0.4 and 1 W/cm 3 .
  • HMDSO hexamethyldisiloxane
  • the treatment time is generally comprised within the range of 20 s - 6 min, and however for a time enabling to obtain a deposited film thickness in the range 10-50 nm.
  • the deposited film follows the shape of the nanostructures and gives to the surface a superhydrophilic character, this means that the water deposited on the surface extends over the entire surface forming a substantially uniform thin layer, or, in other words, that the surface has a contact angle with water that is within zero and 6 degrees and preferably is 0°.
  • the second treatment of the optical element surface surprisingly allows to obtain a surface with superhydrophilic behavior starting from a surface that initially undergoes a treatment, plasma etching, which is normally used to impart hydrophobic properties to such surface.
  • a Polycarbonate slab with dimensions 1.5 cm x 1.5 cm was treated with plasma etching under the following conditions: oxygen flow rate of 10 seem, chamber pressure of 100 mTorr, power density of 0.36 W/cm 3 for a time of 10 min.
  • the resulting nanostructures on the surface have an average size of 400 nm in height with a width of 100 nm and a distance of 300 nm, as measured with a scanning electron microscope.
  • the fogging test was conducted on samples obtained from example 2, the modified sides of the samples were maintained for a time of 3 min on a cylindrical flask with a volume of 2 ml half filled with water and brought to a temperature of 70 ° C. The samples were then observed with white light in transmission with a video camera at low magnification, to determine both the darkening and its duration. While on the untreated samples there was a darkening (blinding) and very persistent fog (depending on the material from 30 s to 2 min) on those modified according to the above described conditions, the formation of a clear liquid was observed which evaporated in few seconds (2 - 8 s). This behavior was also observed after 4 months from the surface treatment on specimens preserved in non-sealed boxes, as well as on specimens tested for several repetitions.
  • Figures 7 and 8 shows the images of the specimens just removed from steam: fig. 7 refers to the sample of untreated PC and fig. 8 to PC treated in the conditions of Example 1 and 2.
  • the untreated PC in Fig. 7 is "opaque" whilst the treated material in Fig. 8 is transparent.
  • the untreated material in Fig. 7 looses fogging in one minute while for the modified (Fig. 8) sample the film of water, transparent, disappeared by evaporation in 5 seconds.
  • the stability of the surfaces having only nanostructures, surfaces having only SiOx film and surfaces having both nanostructures and SiOx film is expressed as ACA values in the graph of figure 9.
  • the measures were carried out on the day of treatment of the surfaces, after 1 month from treatment and after 12 months from treatment; samples were exposed to ambient atmosphere under identical conditions.
  • the graph of fig. 9 shows the importance of the combination of nanostructures and SiOx film in order to reach a stable superhydrophylic effect.
  • the highly hydrophilic affect initially present both on the nanostructured polymer and on the SiOx film (only) is lost in about one month when the element is exposed to ambient air.
  • the procedure object of this invention can be performed on one surface 5, or on both surfaces, 5 and 8, of the transparent polymer 6.
  • it can be combined in order to have on a surface the modification described above and on the other surface a modification aimed to other performances, but anyway based on a plasmochemical nanostructuring process.
  • side 8 of the element is submitted to a process of nanostructuring via plasma etching and to a subsequent deposition of a chemically hydrophobic thin film (SiC x H y , CF X )

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Abstract

L'invention concerne un élément optique comprenant un corps (6) constitué d'une matière plastique transparente et dont au moins l'une des surfaces est modifiée afin de présenter une pluralité de nanostructures (7) directement formées sur la surface (5, 5') du corps (6) ; la surface nanostructurée est au moins partiellement revêtue d'un film (15) de matériau hydrophile, de préférence inorganique, et possède des propriétés superhydrophiles stables dans le temps.
PCT/IB2011/001791 2010-08-09 2011-07-29 Eléments optiques ayant des propriétés hydrophiles et antibuée de longue durée et leur procédé de préparation WO2012020295A1 (fr)

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ITMI2010A001529 2010-08-09
IT001529A ITMI20101529A1 (it) 2010-08-09 2010-08-09 Elementi ottici plastici con caratteristiche antiappannanti e metodo per la loro realizzazione

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WO2012020295A8 WO2012020295A8 (fr) 2012-05-18

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DE102013106392A1 (de) * 2013-06-19 2014-12-24 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung einer Entspiegelungsschicht
JP2016188933A (ja) * 2015-03-30 2016-11-04 長崎県 表面にｄｌｃ膜をコーティングしたモスアイ構造を有する透明基材及びその製造方法
JP2018525688A (ja) * 2015-08-21 2018-09-06 セコ コーポレイション リミテッド プラズマエッチングを用いた反射防止表面の製造方法及び反射防止表面が形成された基板
WO2018234841A1 (fr) * 2017-06-21 2018-12-27 Nikon Corporation Article transparent nanostructuré aux propriétés à la fois hydrophobes et antibuée, et procédés de fabrication
EP3508889A1 (fr) * 2018-01-09 2019-07-10 Danmarks Tekniske Universitet Surface transparente antibuée
WO2021219116A1 (fr) * 2020-04-30 2021-11-04 江苏菲沃泰纳米科技股份有限公司 Couche de film antibuée hydrophile, son procédé de préparation et application et produit de celle-ci
WO2022188639A1 (fr) * 2021-03-12 2022-09-15 江苏菲沃泰纳米科技股份有限公司 Lunettes à couche de film antibuée hydrophile, et procédé de revêtement de film

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JP2018525688A (ja) * 2015-08-21 2018-09-06 セコ コーポレイション リミテッド プラズマエッチングを用いた反射防止表面の製造方法及び反射防止表面が形成された基板
WO2018234841A1 (fr) * 2017-06-21 2018-12-27 Nikon Corporation Article transparent nanostructuré aux propriétés à la fois hydrophobes et antibuée, et procédés de fabrication
JP2020524817A (ja) * 2017-06-21 2020-08-20 株式会社ニコン 疎水特性及び防曇特性の両方を有するナノ構造の透明な物品並びにそれを作製する方法
JP2022188132A (ja) * 2017-06-21 2022-12-20 株式会社ニコン 疎水特性及び防曇特性の両方を有するナノ構造の透明な物品並びにそれを作製する方法
EP3508889A1 (fr) * 2018-01-09 2019-07-10 Danmarks Tekniske Universitet Surface transparente antibuée
WO2021219116A1 (fr) * 2020-04-30 2021-11-04 江苏菲沃泰纳米科技股份有限公司 Couche de film antibuée hydrophile, son procédé de préparation et application et produit de celle-ci
WO2022188639A1 (fr) * 2021-03-12 2022-09-15 江苏菲沃泰纳米科技股份有限公司 Lunettes à couche de film antibuée hydrophile, et procédé de revêtement de film
CN115079317A (zh) * 2021-03-12 2022-09-20 江苏菲沃泰纳米科技股份有限公司 带有亲水防雾膜层的护目镜和镀膜方法

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