WO2021152479A1 - Article nanostructuré - Google Patents

Article nanostructuré Download PDF

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Publication number
WO2021152479A1
WO2021152479A1 PCT/IB2021/050640 IB2021050640W WO2021152479A1 WO 2021152479 A1 WO2021152479 A1 WO 2021152479A1 IB 2021050640 W IB2021050640 W IB 2021050640W WO 2021152479 A1 WO2021152479 A1 WO 2021152479A1
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WO
WIPO (PCT)
Prior art keywords
nanostructures
layer
nanostructured
polymer
substrate
Prior art date
Application number
PCT/IB2021/050640
Other languages
English (en)
Inventor
Peter D. Condo
David Scott Thompson
Chad M. AMB
Moses M. David
Richard J. Pokorny
Thomas P. Klun
Jonah Shaver
Joan M. Noyola
Hannah E. WALSH
Jon P. Nietfeld
John A. Wheatley
Jospeh D. RULE
Ryan M. BRAUN
Michael A. Johnson
Original Assignee
3M Innovative Properties Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Publication of WO2021152479A1 publication Critical patent/WO2021152479A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • FIGS. 18A-18C schematically illustrate integrally forming a nanostructured article with a structural member
  • the nanostructures have steep side walls that may be perpendicular to the substrate or may extend at a predetermined oblique angle to the substrate. In some embodiments, at least a majority of the nanostructures are capped with mask material (e.g., an inorganic silica nanoparticle or an inorganic silica island).
  • mask material e.g., an inorganic silica nanoparticle or an inorganic silica island.
  • the degree of hydrophobicity or omniphobicity can be increased by increasing the fluorine content, for example, in the nanostructured surface.
  • a suitable degree of hydrophobicity or omniphobicity is obtained by nanostructuring a polyurethane or an ionomeric or nanocomposite material as described herein.
  • additional treatments and/or coatings may be applied to the nanostructured surface to make the surface additionally hydrophobic and/or additionally omniphobic.
  • the nanostructured surface is coated with a conformal glass like layer or a diamond like glass (DLG) layer as described further elsewhere herein.
  • Advancing, receding, and static contact angles can be measured with a goniometer. Contact angle measurements are described in 9,085,019 (Zhang et al.), for example.
  • the contact angle hysteresis is the difference between the advancing and receding contact angles.
  • the nanostructured surface has an advancing water contact angle of at least 100 degrees, or at least 120 degrees. In some preferred embodiments, the advancing water contact angle is at least 130 degrees, or at least 140 degrees, or at least 150 degrees, or at least 155 degrees, or even at least 160 degrees. In some embodiments, the static water contact angle is also in one of these ranges.
  • a nanostructured article can include a plurality of polymeric nanostructures defining a nanostructured surface having an advancing water contact angle of at least 130 degrees and an advancing hexadecane contact angle of at least 80 degrees, and at the same time the nanostructured article can have an average optical transmittance of at least 90% and an optical haze of less than 5%.
  • the optical haze is less than 3%, or less than 2%, or less than 1%.
  • the optical haze can be determined as described in the ASTM D 1003- 13 test standard.
  • the optical clarity can be determined according to the ASTM D1746-15 test standard.
  • the average optical transmittance, optical haze and optical clarity may be determined with the nanostructured surface facing toward or away from the light source. In some embodiments, the optical clarity is determined with the nanostructured surface facing away from the light source, and the average optical transmittance and optical haze are determined with the nanostructured surface facing the light source.
  • Luminous transmission, clarity, and haze can be measured using a BYK- Gardner Haze-Gard Plus model 4725 or a BYK-Gardner Haze-Gard i (available from BYK-Gardner Columbia, MD), for example.
  • the first nanostructures may be arranged in a substantially random pattern, a substantially ordered pattern, or in a partially ordered pattern, for example.
  • the first nanostructures may be approximately hexagonally packed posts (e.g., when a high density of posts are present).
  • the average spacing S1 is greater than the average width W1.
  • the average spacing S1 is at least 1.5 times, or at least 2 times or at least 3 times, or at least 4 times the average width W1.
  • the spacing and/or sizes of the nanostructures varies (e.g., randomly) over the nanostructured surface.
  • a coating e.g., a fluorinated and/or low surface energy coating
  • a coating may be disposed over any of the nanostructured surfaces of FIGS. 1 to 6.
  • Such low surface energy coatings may be applied by any suitable method, for example plasma assisted vapor deposition, solvent coating methods, dip coating methods or spray coating methods. Suitable coating materials are described elsewhere herein.
  • a glass like or Diamond Like Glass (DLG) layer e.g., a thin carbon containing silica layer
  • a DLG layer is preferred due to its flexibility and robust adhesion, for example. Processes for depositing DLG layers are described in U.S Pat. Nos.
  • FIG. 8 is a schematic cross-sectional view of a nanostructured article 800 including a substrate 805, a plurality of first nanostructures 803 disposed on, and extending away from, the substrate 805, and a layer 801 (e.g., a fluorinated and/or low surface energy layer) disposed on the plurality of first nanostructures 803 and at least partially filling spaces between the first nanostructures to an average minimum height above the substrate 805 of H0 such that the layer 801 has a nanostructured surface 807 defined by, and facing away from, the plurality of first nanostructures 803.
  • a layer 801 e.g., a fluorinated and/or low surface energy layer
  • the first nanostructures 803 extend to an average height H1 from the substrate 805 (resp., 905) and have an average width W1
  • the nanostructured surface 807 includes a plurality of second nanostructures 808 (resp., 908) having an average peak-to- valley height H2 and an average width W2.
  • H2/W2 is no more than 0.95 H1/W1, or no more than 0.9 H1/W1, or no more than 0.8 H1/W1.
  • H2/W2 is at least 0.1 H1/W1, or at least 0.2 H1/W1, or at least 0.3 H1/W1.
  • L2/W2 is at least 1, 2, 3, 5, 10, or 20, for example. L2/W2 may be in a range of 1 to 100, or 1 to 50, or 3 to 20, for example.
  • Aqueous nanodispersions of unmodified metal oxide nanoparticles may be prepared or, in some embodiments, aqueous nanodispersions of unmodified metal oxide nanoparticles may be obtained commercially.
  • Suitable surface unmodified metal oxide nanoparticles include aqueous nanodispersions commercially available from Nalco Chemical Company (Naperville, IL) under the trade designation ‘Nalco Colloidal Silicas” such as products NALCO 2326, 1130, DVSZN002, 1142, 2327, 1050, DVSZN004, 1060, and 2329K; from Nissan Chemical America Corporation (Houston, TX) under the tradename SNOWTEX such as products ST-NXS, ST-XS, ST-S, ST-30, ST-40, ST-N40, ST-50, ST-XL, and ST-YL; from Nyacol Nano Technologies, Inc.
  • the at least one polymer includes a first polymer including (meth)acrylic acid monomer units and optionally having a number average molecular weight of at least 10000 grams/mole.
  • the first polymer is at least partially neutralized.
  • the metal oxide nanoparticles are surface modified with a carboxylic acid silane surface modifying agent.
  • the carboxylic acid silane surface modifying agent can be or include a carboxylic acid silane of Formula 1, described elsewhere herein.
  • the metal oxide nanoparticles can optionally be omitted when an ionomer layer not including nanoparticles is desired.
  • Covalently crosslinked polyurethanes can provide desired chemical resistance and mechanical robustness (e.g., scratch or abrasion or impact resistant).
  • the polyurethane is a covalently crosslinked aliphatic polyurethane and/or a covalently crosslinked urethane acrylate.
  • Suitable polyurethane materials are described in U.S. Pat. Appl. Pub. Nos. 2017/0170416 (Johnson et al.) and 2017/016590 (Leatherdale et al.), for example.
  • the crosslinked polyurethane layer may then be coated with an aqueous dispersion that is then dried to form an ionomeric or nanocomposite layer of the present disclosure.
  • the crosslinked polyurethane layer can be produced as a film, or as a layer of a film that also includes an ionomeric or nanocomposite layer, that is then laminated to a substrate or glass layer in a subsequent process step. Such lamination could be assisted with heat, or vacuum, or through the use of an adhesive, or a combination thereof.
  • the substrate or glass layer may be substantially transparent (e.g., an average optical transmittance of at least 60%, or at least 70%, or at least 80%, or at least 90%).
  • dibutyltin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin dimercaptide, dibutyltin dioctoate, dibutyltin dimaleate, dibutyltin acetonylacetonate, and dibutyltin oxide.
  • dibutyltin dilaurate catalyst DABCO T-12 commercially available from Air Products and Chemicals, Inc., Allentown, PA is suitable.
  • the catalyst is typically included at levels of at least 200 ppm or even 300 ppm or greater.
  • the catalyst may be present in the final formed films at levels of at least 100 ppm or in a range from 100-500 ppm, for example.
  • the crosslink concentration and the gel content of the cured polyurethane can be calculated using the method described in Macromolecules, Vol. 9, No. 2, pages 206-211 (1976). To implement this model, integral values for chemical functionality are used. DESMODURN3300 is reported to have an average functionality of 3.5 and an isocyanate equivalent weight of 193 g/equiv. This material was represented in the mathematical model as a mixture of 47.5 wt% HDI trimer (168.2 g/equiv.), 25.0 wt% HDI tetramer (210.2 g/equiv.), and 27.5 wt% of HDI pentamer (235.5 g/equiv.). This mixture yields an average equivalent weight of 193 g/equiv.
  • Suitable fluorochemical coatings include 3M EASY CLEAN COATING ECC-1000, 3M EASY CLEAN COATING ECC-4000, 3M NOVEC 1720 ELECTRONIC GRADE COATING, and 3M NOVEC 2202 ELECTRONIC GRADE COATING, available from 3M Company (St. Paul, MN).
  • dibutyl tin dilaurate dibutyl tin diacetate, dibutyl tin dichloride, dibutyl tin dibromide, dibutyl tin bis(acetylacetonate), dibutyl tin dioxide, dibutyl tin dioctoate, tin (II) octoate, tin (II) neodecanoate, tetraisopropoxy titanium, tetra -n- butoxytitanium, titanium tetrakis(2 - ethylhexoxy), triethanolamine titanate chelate, titanium diisopropoxide (bis-2,4- pentanedionate), aluminum tris(acetylacetonate), aluminum titanate, zinc ethylhexanoate, K-Kat 670 (King Industries, Norwalk CT).
  • Useful nominally colorless polyimide films may have glass transition temperatures greater 220 degrees Celsius or greater than 250 degrees Celsius or even greater than 300 degrees Celsius and tensile moduli greater than 6GPa, or greater than 6.5GPa or even Greater than 7GPa. These high modulus polymers exhibit excellent resistance to plastic deformation.
  • the polyimide is nominally colorless in that the b* value for the film is no more than 5. In some preferred cases, b* is no more than 4, or no more than 3, or no more than 2.
  • the first layer 1405a has a fluorine concentration of at least 5%, or at least 10 wt%, or at least 20 wt%, or at least 30 wt%. In some such embodiments or in other embodiments, the second and third layers 1405b and 1410 are not fluorinated or have a fluorine concentration of less than 3% on an atomic basis. In some embodiments, the first layer 1405a is a fluorinated polyurethane hardcoat.
  • layer 1605a is a fluorinated polyurethane layer
  • layer 1605b is an ionomeric or nanocomposite layer
  • layer 1610 is a polyurethane layer.
  • layer 1605a is a fluorinated polyurethane layer
  • layer 1605b is a polyurethane layer
  • layer 1610 is an ionomeric or nanocomposite layer.
  • layers 1605a and 1605b are replaced with a single nanocomposite layer and layer 1610 is a polyurethane layer or an ionomeric layer or a nanocomposite layer.
  • Layers 1605a, 1605b and 1610 can be as described elsewhere for any embodiments of layers 1405a, 1405b, and 1410, for example.
  • the thickness of the layers 1605a or 1605b or a combined thickness of the layers 1605a and 1605b may be in a range of 1 to 50 micrometers, or 2 to 20 micrometers, or 3 to 13 micrometers, for example.
  • the thickness of the layers 1610 or 1620 or a combined thickness of the layers 1610 and 1620 may be in a range of 50 to 500 micrometers, or to 200 micrometers, or to 150 micrometers, or to 100 micrometers, for example.
  • the thickness of the layer 1607 may be in a range of 50 nm to 1 micrometer, or 80 nm to 500 nm, or 80 nm to 200 nm, for example.
  • the layer 1620 may have a yield stress value greater than 70 MPa, or greater than 90 MPa, or greater than 120 MPa, or greater than 160 MPa.
  • the yield stress in this context refers to the 0.2% offset yield stress and can be determined according to the ASTM D638-14 test standard, for example.
  • the layer 1620 may be formed of any useful polymeric material that provides the desired mechanical properties (such as dimensional stability) and optical properties (such as light transmission and clarity). Examples of materials suitable for use in the layer 1620 include polymethylmethacrylate, polycarbonate, polyamides, polyimide, polyesters (e.g., polyethylene terephthalate (PET), polyethylene naphthalate (PEN)), polycyclic olefin polymers, and thermoplastic polyurethanes.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the layer 1620 may include a multilayer optical film construction which has desired optical functions or properties.
  • the optical film may include a wavelength selective filter.
  • the layer 1620 may be or include a colored film that may be partially transparent or non- transparent film.
  • the film may be a white or colored film.
  • the average optical transmittance, optical haze and/or optical clarity is in any of these ranges after the nanostructured surface of the nanostructured article 1600 has been abraded for 10 cycles at a rate of 60 cycles/min with an AATCC (American Association of Textile Chemists and Colorists) Crockmeter Standard Rubbing Cloth using a 1-inch diameter circular abrading head and a 350 g force, as described further in the Examples.
  • the nanostructured surface may have contact angles (advancing or receding, for water or for hexadecane) in any of the ranges described elsewhere herein, and/or water roll- off angles in any of the ranges described elsewhere herein, before and after it has been abraded.
  • the nanostructured article is disposed on, and integrally formed with, a structural member.
  • a first element “integrally formed” with a second element means that the first and second elements are manufactured together rather than manufactured separately and then subsequently joined. Integrally formed includes manufacturing the second element followed by manufacturing the first element on the second element.
  • the nanostructures may extend generally along a same direction that is not normal to at least portions of the curved surface.
  • the direction that the nanostructures extend can be controlled by the etching technique used to make the nanostructures (e.g., in embodiments where the nanostructures are formed by reactive ion etching, the direction of the nanostructures can be controlled by controlling the direction of the ion beam).
  • the nanostructured surface of the nanostructured article is patterned such that some regions of the surface include the nanostructures and other regions do not.
  • melt-processed material is pressed into a film using an Auto Series Hot Press (Carver Inc., Wabash, IN).
  • a portion of the melt- processed film is placed between two layers of polyimide film which are between two polished aluminum plates.
  • the melt-processed material was pressed to 900 kg force at 125°C and held for 5 minutes.
  • the sample was then pressed to 10900 kg force at 125°C and held for 0.1 minutes (6 seconds).
  • the pressed film is removed from the press and from between the aluminum plates and cooled to room temperature.
  • the polyimide sheets are removed once the film sufficiently cooled.
  • the thickness of the pressed film is ⁇ 100 microns and the film is expected to have a Transmission of >92%, Haze of ⁇ 4.0%, and Clarity of >90%.
  • This pressed film example demonstrates the properties of the film.
  • a film of controlled thickness for example a film having a thickness of 100 microns, may be made via known extrusion casting and orientation methods to produce rolls of monolithic film which can be used in roll to roll processing.
  • a sample of shape memory polyurethane with an NCO/OH ratio of 1.05 is prepared in a roll to roll process where the isocyanate and polyol with catalyst are mixed using an inline dynamic mixer.
  • the solutions are applied to a moving web between a silicone release liners and an approximately 100 ⁇ m thick ionic elastomer nanocomposite film as described above with 5wt% 20nm SiO 2 nanoparticles.
  • the surface of the Ionic elastomer nanocomposite is activated with an atmospheric plasma.
  • the mixed solutions are delivered at an appropriate flow rate to achieve the desired final sample thickness of -100 ⁇ m of shape memory polyurethane.
  • the polyurethane between films are heated at 70°C and wound into a roll.
  • the thickness of the pressed film was 3.5 mil ( ⁇ 89 microns) and the film had a Transmission of 93.4%, Haze of 3.6%, and Clarity of 94.7%.
  • Films of controlled thickness may be made via known extrusion casting and orientation methods to produce rolls of monolithic film at thickness from 25-250 microns.
  • the solution is applied to the above hardcoated/etched/DLG film in a roll to roll process where the solution is metered through a slot die onto the moving web. Thickness is controlled by the use of a syringe pump.
  • the volatile components of the coating is removed by drying in a two-zone oven (oven temperatures set to 93°C, 93°C).
  • the dried and cured coating has a thickness of approximately 100 nm.
  • the nanostructured film constructions described in the above examples with nanostructured Ionic elastomer and ionic elastomer nanocomposite overcoated with highly fluorinated coatings may use any suitable polyurethane substrate described herein as a base substrate.
  • a HFPO UA hardcoat is disposed on an ionic elastomer nanocomposite substrate and the HFPO UA HC is etched and overcoated with a highly fluorinated herein may use any suitable Ionic Elastomer Nanocomposite substrate.
  • the substrates described in the Preparatory Film Substrates S21 - S25 may be used.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un article nanostructuré (800) comprenant un substrat ; une pluralité de premières nanostructures (803) agencées sur le substrat et s'étendant à l'opposé de celui-ci ; et une couche polymère fluorée réticulée (801) agencée sur la pluralité de premières nanostructures (803). La pluralité de premières nanostructures (803) comprend au moins un polymère qui comprend un premier polymère comprenant des motifs monomères d'acide (méth)acrylique. La couche polymère remplit au moins partiellement des espaces entre les premières nanostructures (803) à une hauteur minimale moyenne au-dessus du substrat d'au moins 30 nm de sorte que la couche polymère présente une surface nanostructurée (807) définie par la pluralité de premières nanostructures et tournée à l'opposé de la pluralité de celles-ci (803).
PCT/IB2021/050640 2020-01-29 2021-01-27 Article nanostructuré WO2021152479A1 (fr)

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US202062967446P 2020-01-29 2020-01-29
US62/967,446 2020-01-29

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US20170067150A1 (en) * 2013-07-26 2017-03-09 3M Innovative Properties Company Method of making a nanostructure and nanostructured articles
US20170227682A1 (en) * 2014-01-20 2017-08-10 3M Innovative Properties Company Lamination transfer films for forming antireflective structures
US20180229420A1 (en) * 2015-08-10 2018-08-16 Essilor International Article having a nanotextured surface with hydrophobic properties
US20180237291A1 (en) * 2015-08-14 2018-08-23 Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E. V. Fabrication of nanostructured substrates comprising a plurality of nanostructure gradients on a single substrate
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

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* Cited by examiner, † Cited by third party
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US5674592A (en) * 1995-05-04 1997-10-07 Minnesota Mining And Manufacturing Company Functionalized nanostructured films
JP2001207123A (ja) * 1999-11-16 2001-07-31 Sentan Kagaku Gijutsu Incubation Center:Kk 高硬度高滑水性膜およびその製造方法
US20070028588A1 (en) * 2005-08-03 2007-02-08 General Electric Company Heat transfer apparatus and systems including the apparatus
US20070141114A1 (en) * 2005-12-15 2007-06-21 Essilor International Compagnie Generale D'optique Article coated with an ultra high hydrophobic film and process for obtaining same
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JP2012077147A (ja) * 2010-09-30 2012-04-19 Lintec Corp 撥水シート
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US20130230695A1 (en) * 2010-11-08 2013-09-05 University Of Florida Research Foundation, Inc. Articles having superhydrophobic and oleophobic surfaces
US20140166100A1 (en) * 2011-05-25 2014-06-19 Hitachi, Ltd. Solar cell
JP2013003383A (ja) * 2011-06-17 2013-01-07 Nissan Motor Co Ltd 耐摩耗性微細構造体及びその製造方法
JP2014113721A (ja) * 2012-12-07 2014-06-26 Denki Kagaku Kogyo Kk 撥水性を付与した積層シート及びラミネート用フィルム
US20150306852A1 (en) * 2012-12-07 2015-10-29 Denki Kagaku Kogyo Kabushiki Kaisha Water-repellent, thermoplastic resin sheet, and molded article
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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

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