WO2014061606A1 - Film antireflet antisalissure, article, et procédé de fabrication de ce film et de cet article - Google Patents

Film antireflet antisalissure, article, et procédé de fabrication de ce film et de cet article Download PDF

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Publication number
WO2014061606A1
WO2014061606A1 PCT/JP2013/077817 JP2013077817W WO2014061606A1 WO 2014061606 A1 WO2014061606 A1 WO 2014061606A1 JP 2013077817 W JP2013077817 W JP 2013077817W WO 2014061606 A1 WO2014061606 A1 WO 2014061606A1
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Prior art keywords
nanosheet
antifouling
antifouling layer
silica
film
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PCT/JP2013/077817
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English (en)
Japanese (ja)
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拓紀 松尾
洋平 河合
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旭硝子株式会社
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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
    • G02B1/11—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
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D5/006—Anti-reflective coatings
    • 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
    • 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
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
    • H02S40/10—Cleaning arrangements
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
    • H02S40/20—Optical components
    • H02S40/22—Light-reflecting or light-concentrating means
    • 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
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/732—Anti-reflective coatings with specific characteristics made of a single layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Definitions

  • the present invention relates to an antifouling antireflection film, an article provided with the antifouling antireflection film, and a method for producing the same.
  • Articles having an antireflection film on the surface of a transparent substrate such as a glass plate are used as cover members for solar cells, various displays and their front plates, various window glasses, touch panel cover members, and the like.
  • the antireflection film is disposed on the outermost layer of the article because of its function. For this reason, the antireflection film is required to have antifouling properties (that is, it is difficult for dirt to adhere to it and it can be easily removed even if it adheres).
  • an antireflection film used for a transparent substrate such as a glass plate is a silica-based porous film (see, for example, Patent Document 1). Since the silica-based porous film has pores in a matrix containing silica as a main component, the refractive index is lower than that in the case where there are no pores. However, since the silica-based porous film has many fine open holes and irregularities on the surface, there are problems that dirt such as oil dirt and resin is likely to adhere, and that the attached dirt is difficult to remove. For example, in the manufacturing process of the solar cell, a step of bonding the cover member and the solar cell with a sealing material is performed.
  • EVA ethylene-vinyl acetate copolymer resin
  • a sealing material soaks into the silica-based porous film during the manufacturing process, and antireflection performance is improved.
  • the soaked EVA is difficult to peel off from the silica-based porous film, and even after peeling, the color of the silica-based porous film where the EVA has soaked becomes different from the other parts.
  • problems such as.
  • a protective film is provided on a silica-based porous film.
  • the method of providing the protective film increases the cost.
  • a method of applying a fluorine-based coating agent to the surface of a silica-based porous film has also been proposed (see, for example, Patent Document 2).
  • the method of applying a fluorine-based coating agent can improve the antifouling property against oil stains and EVA easily and at a lower cost than when a protective film is provided.
  • the coating agent there is a concern that the antireflection performance may be deteriorated by dipping into the silica-based porous film during coating.
  • the silica-based porous film imparted with the antifouling property by the above method is likely to remain after being installed as a solar cell module outdoors due to water repellency, and dirt is not scattered evenly due to rainwater. For example, it is difficult to maintain a good appearance for a long time.
  • the present invention has been made in view of the above circumstances, and has improved antifouling properties while maintaining the antireflection performance of the silica-based porous film, and the antifouling antireflection film capable of maintaining a good appearance over a long period of time,
  • An object is to provide an article provided with an antifouling antireflection film and a method for producing the same.
  • the present invention has the following aspects.
  • the antifouling layer contains a plurality of nanosheets, and the nanosheets are made of a low refractive material having a refractive index of 1.4 to 1.65,
  • a step of forming a silica-based porous film on a transparent substrate Applying a coating solution for forming an antifouling layer to the surface of the silica-based porous membrane, and drying to form an antifouling layer
  • the antifouling layer forming coating solution contains a plurality of nanosheets and a dispersion medium of the nanosheets,
  • the nanosheet is made of a low refractive material having a refractive index of 1.4 to 1.65
  • a method for producing an article having an antifouling antireflection film, wherein an antifouling antireflection film having an average film thickness of 0.4 to 40 nm is formed.
  • the nanosheets has a mean average area of thickness and 100 ⁇ 1,000,000 2 of 0.7 ⁇ 20 nm, method of making an article according to [6].
  • the antifouling layer forming solution coating solution further includes a binder or a precursor thereof, and the nanosheet content relative to the total amount of the nanosheet and the binder or the precursor thereof in the antifouling layer forming coating solution.
  • the dispersion medium contains water, and the water content in the antifouling layer forming coating solution is 60% by mass or less based on the total mass of the antifouling layer forming coating solution.
  • the antifouling antireflection film capable of maintaining a good appearance over a long period of time while improving the antifouling property while maintaining the antireflection performance of the silica-based porous film and the antifouling antireflection film are provided. Articles and methods for manufacturing the same can be provided.
  • Example 2 It is a schematic sectional drawing which shows one Embodiment of the articles
  • Example It is the SEM photograph of the outermost surface by the side of the silica type porous membrane of the glass plate with a silica type porous membrane before forming an antifouling layer produced in Example 2 in FIG. It is a SEM photograph ((a) outermost surface on the antifouling layer side, (b) cross section) of the article obtained in Example 2.
  • FIG. 1 is a cross-sectional view showing a first embodiment of an article having the antifouling antireflection film of the present invention on a transparent substrate.
  • the article 10 of the present embodiment includes a transparent base material 12 and an antifouling antireflection film 18 formed on the surface of the transparent base material 12.
  • the antifouling antireflection film 18 comprises a silica-based porous film 14 and an antifouling layer 16 formed on the surface of the silica-based porous film 14.
  • Transparent substrate 12 Examples of the shape of the transparent substrate 12 include a plate and a film. Examples of the material of the transparent substrate 12 include glass and resin. Examples of the glass include soda lime glass, borosilicate glass, aluminosilicate glass, and alkali-free glass. Examples of the resin include polyethylene terephthalate, polycarbonate, triacetyl cellulose, polymethyl methacrylate, and the like.
  • the transparent substrate 12 a glass plate is preferable.
  • the glass plate may be a smooth glass plate formed by a float method or the like, or may be a template glass having irregularities on the surface. Moreover, not only a flat glass plate but the glass plate which has a curved surface shape may be sufficient.
  • the thickness of the glass plate is not particularly limited, and a glass plate having a thickness of 0.2 to 10 mm can be used. The thinner the thickness, the lower the light absorption, which is preferable for the purpose of improving the transmittance.
  • oxide-based mass percentage display (hereinafter, “mass percentage display” is also simply referred to as “%”, hereinafter the same).
  • SiO 2 65 to 75%
  • Al 2 O 3 0 to 10%
  • CaO 5 to 15%
  • MgO 0 to 15%
  • K 2 O 0 to 3%
  • Fe 2 O 3 0 to 3%
  • TiO 2 0 to 5%
  • CeO 2 0 to 3%
  • BaO 0 to 5%
  • SrO: 0-5% B 2 O 3 : 0 to 15%
  • ZrO 2 0 to 5%
  • SnO 2 : 0 to 3% SO 3 : 0 to 0.5%.
  • a glass plate is an alkali free glass
  • what has the following composition is preferable.
  • SiO 2 39 to 70%
  • Al 2 O 3 3 to 25%
  • B 2 O 3 1-30%
  • MgO 0 to 10%
  • CaO 0 to 17%
  • SrO 0 to 20%
  • BaO 0 to 30%.
  • the glass plate is a mixed alkali glass
  • those having the following composition are preferred.
  • SiO 2 50 to 75%
  • Al 2 O 3 0 to 15%
  • MgO + CaO + SrO + BaO + ZnO 6 to 24%
  • Na 2 O + K 2 O 6-24%.
  • the glass plate is a cover glass for solar cells
  • a satin-patterned template glass with an uneven surface is preferable.
  • iron component ratio is smaller than soda lime glass (so-called soda lime glass: common name of soda lime glass with a slight bluish tint) used for ordinary window glass, etc.
  • Soda lime glass is preferable.
  • a functional layer may be formed on the surface of the transparent substrate 12 in advance.
  • the functional layer include an undercoat layer, an adhesion improving layer, and a protective layer.
  • the undercoat layer include those having a function as an alkali barrier layer or a wide band low refractive index layer.
  • the undercoat layer is preferably a layer formed by applying an undercoat coating composition containing a hydrolyzate of alkoxysilane (silane hydrolysis sol) on a substrate. When applying the topcoat liquid mentioned later on an undercoat layer, the undercoat layer may be baked beforehand and may remain in a wet state.
  • the coating temperature is preferably room temperature to 80 ° C.
  • the firing temperature is preferably 30 to 700 ° C.
  • the thickness of the undercoat layer is preferably 10 to 500 nm.
  • the “silica-based porous membrane” is a membrane having a plurality of pores in a matrix mainly composed of silica.
  • the silica-based porous film has a relatively low refractive index and a low reflectance because the matrix is mainly composed of silica.
  • Such a silica-based porous film is excellent in chemical stability, adhesion to a transparent substrate 12 such as a glass plate, and wear resistance. Furthermore, by having holes in the matrix, the refractive index is lower than when there are no holes.
  • That the matrix is mainly composed of silica means that the proportion of silica is 90% by mass or more of the matrix (100% by mass).
  • a matrix what consists essentially of silica is preferable.
  • the phrase “substantially composed of silica” means that it is composed only of silica excluding inevitable impurities (for example, a structure derived from the compound (a2) described later).
  • the matrix may contain a small amount of components other than silica.
  • the components include Li, B, C, N, F, Na, Mg, Al, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Sr.
  • the matrix may include not only two-dimensionally polymerized matrix components but also three-dimensionally polymerized nanoparticles.
  • the composition of the nanoparticles include Al 2 O 3 , SiO 2 , SnO 2 , TiO 2 , ZnO, and ZrO 2 .
  • the size of the nanoparticles is preferably 1 to 100 nm.
  • the shape of the nanoparticles is not particularly limited, and examples thereof include a spherical shape, a needle shape, a hollow shape, a sheet shape, and a square shape.
  • the ratio of the nanoparticles is preferably 20% by mass or less with respect to the matrix solid content. Within this range, sufficient film strength is maintained.
  • the silica-based porous film 14 is not particularly limited, and a known silica-based porous film can be used.
  • a dispersion medium (a) fine particles (b) dispersed in the dispersion medium (a), and a matrix precursor (c) dissolved or dispersed in the dispersion medium (a) )
  • a film obtained by baking As the matrix precursor (c), a hydrolyzate of alkoxysilane is used.
  • the film is a film in which fine particles (b) are dispersed in a matrix made of a fired product (SiO 2 ) of a matrix precursor (c).
  • the film exhibits an antireflection effect by voids selectively formed around the fine particles (b). In particular, when the core part of the fine particles (b) is hollow, a more excellent antireflection effect is exhibited.
  • the coating liquid and a method for forming a silica-based porous film using the coating liquid will be described in detail later.
  • the film thickness of the silica-based porous film 14 is preferably 50 to 300 nm, and more preferably 80 to 200 nm. When the thickness of the silica-based porous film 14 is 50 nm or more, light interference occurs and antireflection performance is exhibited. If the thickness of the silica-based porous film 14 is 300 nm or less, the film can be formed without generating cracks. The film thickness of the silica-based porous film 14 is measured by a reflection spectral film thickness meter.
  • the surface of the porous silica membrane 14 preferably has open holes.
  • the article 10 of the present embodiment is exposed to ultraviolet rays or wind and rain outdoors to remove the antifouling layer, if the surface has an open hole, it tends to be a hydrophilic surface, and dirt such as sand and dust is caused by rainwater or the like. It becomes easy to flow down evenly.
  • the antifouling layer 16 contains a plurality of nanosheets.
  • Each of the plurality of nanosheets is made of a low refractive material having a refractive index of 1.4 to 1.65.
  • the refractive index of the low refractive material is 1.4 to 1.65, preferably 1.4 to 1.6.
  • the refractive index of the low refractive material constituting the nanosheet is a value obtained by calculating from the reflectance obtained by spectral reflectance measurement.
  • the antifouling layer 16 is formed by applying an antifouling layer forming coating solution in which a plurality of nanosheets are dispersed in a liquid medium to the surface of the silica-based porous film 14 and drying it.
  • an antifouling layer forming coating solution in which a plurality of nanosheets are dispersed in a liquid medium to the surface of the silica-based porous film 14 and drying it.
  • the nanosheet is contained and the content is equal to or greater than a predetermined amount, the nanosheet is deposited on the openings and irregularities on the surface of the porous silica film 14 when the antifouling layer forming coating solution is applied. To do.
  • the penetration of the liquid medium of the antifouling layer forming coating liquid into the silica-based porous film 14 is also suppressed, and even when an optional component such as a binder is dissolved in the liquid medium, the optional component is silica-based. It is difficult for the antireflection performance to deteriorate due to soaking in the porous film 14. And since the antifouling layer 16 formed by depositing a plurality of nanosheets is dense and has high surface smoothness compared to the silica-based porous film 14, it is difficult for dirt to enter. Therefore, it is difficult for dirt to adhere, and even if dirt is attached, it is easy to remove.
  • the nanosheet is made of a low refractive material and the total thickness of the antifouling layer is thin, it is denser than the silica-based porous film, but hardly affects the antireflection performance of the silica-based porous film 14.
  • the low refractive material having a refractive index of 1.4 to 1.65 may be any material as long as the refractive index is within the above range, and can be appropriately selected from known nanosheets.
  • the nanosheet made of the low refractive index material includes at least one inorganic layered compound selected from the group consisting of layered polysilicate (refractive index 1.45) and clay mineral (refractive index 1.56 to 1.58). Those derived are preferred.
  • the nanosheet derived from the inorganic layered compound has a lower hydrophobicity than the fluorine-based coating agent, and has a relatively low water repellency on the surface of the antifouling layer formed.
  • the inorganic layered compound has a structure in which a plurality of nanosheets are laminated, and natural products and synthetic products are commercially available. A nanosheet can be obtained by peeling off the layer constituting the inorganic layered compound.
  • the clay mineral means one having an octahedral structure such as AlO 6 in the crystal structure, and the layered polysilicate is different from the clay mineral in that it does not have the octahedral structure.
  • Examples of the layered polysilicate include kanemite, macatite, magadiite, kenyanite, octosilicate and the like.
  • the composition of the layered polysilicate can be represented by the following composition formula (i).
  • Examples of the alkali metal atom in M include Na, K, and Li. M 2 O.xSiO 2 .yH 2 O (i) In the formula, M is an alkali metal atom, x is an integer of 2 to 40, and y is an integer of 1 to 20.
  • clay minerals examples include smectite, vermiculite, layered double hydroxide (LDH), and the like.
  • smectite examples include 2-octahedron type (saponite, hectorite, etc.) and 3-octahedron type (montmorillonite, beidellite, etc.).
  • composition of 2-octahedral smectite can be represented by the following composition formula (ii) (including interlayer cations).
  • composition of 3-octahedral smectite can be represented by the following composition formula (iii) (including intercalation cations).
  • M 1 to M 4 are each independently an alkali metal atom, an alkaline earth metal atom or a transition metal atom.
  • alkali metal atom examples include Mg and Ca.
  • transition metal atoms include Fe and Al.
  • composition of vermiculite can be represented by the following composition formula (iv). (Mg, Fe, Al) 3 (Al, Si) 4 O 10 (OH) 2 .4H 2 O ... (iv)
  • the composition of LDH can be represented by the following composition formula (v) (including interlayer anions).
  • M 5 is a divalent metal ion (Mg 2+ , Ca 2+ , Zn 2+ , Ni 2+ etc.)
  • M 6 is a trivalent metal ion (Al 3+ , Fe 3+ , Cr 3+ etc.)
  • A is an n-valent anion
  • n is an integer of 1 to 3.
  • Examples of A include Cl ⁇ , NO 3 ⁇ , CO 3 2 ⁇ and the like.
  • the inorganic layered compound is preferably a clay mineral, and particularly preferably smectite.
  • the layered polysilicate hydroxyl groups are exposed on the layer surface, whereas in the clay mineral, hydroxyl groups are not exposed on the layer surface.
  • the nanosheet obtained from the clay mineral has weak adhesion to the silica-based porous film 14, and the antifouling layer 16 is easily washed away by exposure outdoors. By eliminating the antifouling layer 16 over time, the low-reflective property of the silica-based porous film 14 is sufficiently developed.
  • the surface of the porous silica membrane 14 has open holes, when the article 10 is exposed to ultraviolet rays or wind and rain outdoors to remove the antifouling layer and the porous silica membrane 14 is exposed,
  • the outermost surface of the article 10 is likely to be a hydrophilic surface, and dirt such as sand and dust is likely to flow evenly with rainwater or the like. Therefore, a good appearance can be maintained over a long period.
  • titanium oxides such as Ti 0.91 O 2 and Ti 1.73 Li 0.27 O 2
  • manganese oxides such as MnO 2
  • oxidations such as Nb 6 O 17 and Nb 3 O 8, etc.
  • Transition metal oxides such as niobium and tungsten oxides such as WO 3 ; transition metal chalcogenides such as MoS 2 ; layered perovskites such as Ca 2 Nb 3 O 10 and La 2 Nb 2 O 7
  • these materials have low transparency or are transparent but have a high refractive index. Therefore, when a nanosheet derived from these materials is used for the antifouling layer, the antireflection performance is lowered, which is not preferable.
  • the average thickness of the plurality of nanosheets contained in the antifouling layer is preferably 0.7 to 20 nm, more preferably 0.7 to 15 nm, and even more preferably 0.7 to 10 nm. If the average thickness of the nanosheet is 0.7 nm or more, the structure of the individual nanosheets is not easily destroyed, and the durability of the antifouling layer is increased. If the average thickness of the nanosheet is 20 nm or less, it is easy to form a thin antifouling layer, for example, an antifouling layer having an average thickness of 40 nm or less.
  • Area of the plurality of the nanosheet contained in the antifouling layer is preferably 100 nm 2 or more, more preferably 200 nm 2 or more, more preferably 400 nm 2 or more. If the area of the nanosheet is 100 nm 2 or more, when the antifouling layer forming coating solution described later is applied to form the antifouling layer, the nanosheet is less likely to enter the silica-based porous film 14, and the silica-based porous The surface of the membrane is successfully coated with nanosheets.
  • the upper limit of the area of nanosheets is not particularly limited, dispersibility in an antifouling layer forming coating solution, considering the easy availability and the like, preferably 1,000,000 2 or less, and more is 250,000Nm 2 or less preferable.
  • the nanosheet preferably has an average thickness of 0.7 to 20 nm and an average area of 100 to 1,000,000 nm 2 , and an average thickness of 0.7 to 15 nm and 200 to 200 nm. more preferably those having an average area of 1,000,000 2, more preferably those having an average average area of thickness and 200 ⁇ 250,000nm 2 of 0.7 ⁇ 10 nm.
  • the nanosheet may be a nanosheet surface-modified with a treatment agent such as a surfactant, and the nanosheet may contain a nanosheet surface-modified with a treatment agent such as a surfactant.
  • a treatment agent such as a surfactant
  • the nanosheet may contain a nanosheet surface-modified with a treatment agent such as a surfactant.
  • Surfactants include alkyl carboxylic acid salts such as sodium octoate, potassium octoate, sodium decanoate, potassium decanoate, sodium laurate, potassium laurate, sodium stearate, potassium stearate, sodium hexanesulfonate, hexane
  • Alkyl sulfonates such as potassium sulfonate, sodium octane sulfonate, potassium octane sulfonate, sodium decane sulfonate, potassium decane sulfonate, sodium dodecane sulfonate, potassium dodecane sulfonate; sodium lauryl sulfate, potassium lauryl sulfate, myristyl sulfate Sulfate esters such as sodium and potassium myristyl sulfate, phosphate esters such as sodium lauryl phosphate and sodium tripolyphosphate, tetramethylam
  • Treatment agents other than surfactants include trimethylsilyl chloride, triethylsilyl chloride, t-butyldimethylsilane, tri-i-propylsilyl chloride, chloromethyltrimethylsilane, triethylsilane, butyldimethylsilane, trimethylvinylsilane, allyltrimethylsilane, Examples of the silylating agent include hexamethyldisilazane.
  • this peeling may be performed in water containing a surfactant.
  • the nanosheet dispersion liquid thus obtained contains nanosheets surface-modified with a surfactant.
  • the nanosheet contained in the antifouling layer 16 may be one type or two or more types.
  • the antifouling layer 16 may contain a binder in addition to the nanosheet.
  • a binder By including a binder, the adhesion between the plurality of nanosheets, the denseness of the antifouling layer 16, the removability of the antifouling layer 16 when exposed outdoors, and the like can be improved.
  • the binder itself or its precursor is preferably water-soluble.
  • a water-soluble polymer is more preferable as the binder.
  • the water-soluble polymer is easily deteriorated by ultraviolet rays, wind and rain, etc. when exposed outdoors, and therefore has an effect of improving the removal property of the antifouling layer 16.
  • the hydrolyzable silane compound is represented by, for example, SiX m Y 4-m (where m is an integer of 2 to 4, X is a hydrolyzable group, and Y is a non-hydrolyzable group).
  • the hydrolyzate of the hydrolyzable silane compound has a structure in which the Si—X group of SiX m Y 4-m becomes Si—OH by hydrolysis, and Si—OH can be bonded to the nanosheet surface.
  • the hydrolyzate can bind nanosheets by having two or more Si—OH.
  • hydrolyzate may condense and form a condensate.
  • the hydrolyzable group of X is a group that can convert a Si—X group into a Si—OH group by hydrolysis.
  • the hydrolyzable group include a halogen atom (for example, a chlorine atom), an alkoxy group, an acyloxy group, an aminoxy group, an amide group, a ketoximate group, a hydroxyl group, an epoxy group, a glycidyl group, and an isocyanate group, and an alkoxy group is particularly preferable.
  • the non-hydrolyzable group of Y is a functional group whose structure does not change under the condition that the Si—X group becomes a Si—OH group by hydrolysis.
  • the non-hydrolyzable group is not particularly limited, and may be a known group as a non-hydrolyzable group in a silane coupling agent or the like.
  • hydrolyzable silane compounds include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.), alkoxysilane having an alkyl group (methyltrimethoxysilane, methyltriethoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, etc.), alkoxysilanes having aryl groups (phenyltrimethoxysilane, phenyltriethoxysilane, etc.) , Alkoxysilane having a perfluoropolyether group (perfluoropolyether triethoxysilane, etc.), alkoxysilane,
  • tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane are preferable.
  • an alkoxysilane having an alkyl group or an alkoxysilane having a perfluoroalkyl group is preferable.
  • Hydrolysis of the hydrolyzable silane compound is carried out by an amount of water that can hydrolyze all the hydrolyzable groups of the hydrolyzable silane compound (for example, in the case of tetraalkoxysilane, four times or more moles of water of tetraalkoxysilane), and a catalyst.
  • a catalyst As an acid or alkali.
  • the acid include inorganic acids (HNO 3 , H 2 SO 4 , HCl, etc.) and organic acids (formic acid, oxalic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, etc.).
  • the alkali include ammonia, sodium hydroxide, potassium hydroxide and the like.
  • the catalyst is preferably an acid from the viewpoint of long-term storage. Moreover, as a catalyst, what does not disturb dispersion
  • water-soluble polymer examples include polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, polyethylene imine, polydiallyl dimethyl ammonium chloride, sodium polyacrylate, polyacrylamide, polylactic acid, sodium polystyrene sulfonate, sodium polyvinyl sulfate, carboxy Vinyl polymer, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, guar gum, cationized guar gum, carrageenan, sodium alginate, corn starch, xanthan gum, sodium chondroitin sulfate, sodium hyaluronate, starch, modified starch, glue, gelatin, gum arabic, sodium alginate, pectin Etc.
  • the molecular weight of the water-soluble polymer is preferably 1,000 to 100,000. When the molecular weight is less than 1,000, the water-soluble polymer is likely to enter the inside of the silica-based porous film 14 and the transmittance is likely to decrease. When the molecular weight is larger than 100,000, it is difficult to dissolve in a solvent, and nanosheets and aggregates are generated in the paint, which may reduce the stability of the paint.
  • the antifouling layer 16 may contain other components other than the nanosheet and the binder as needed, as long as the effects of the present invention are not impaired.
  • the other components include surfactants that do not modify the surface of the nanosheet, silica fine particles, and titania fine particles. In the case of containing titania fine particles, it is expected that the attached dirt is decomposed by the photocatalytic effect.
  • the average film thickness of the antifouling layer 16 is 0.4 to 40 nm, preferably 1 to 20 nm. Sufficient antifouling property is acquired as the average film thickness of the antifouling layer 16 is 0.4 nm or more. When it is 40 nm or less, the antifouling layer 16 has little influence on the antireflection performance of the silica-based porous film 14, and the decrease in maximum transmittance due to the provision of the antifouling layer 16 can be suppressed.
  • the measuring method of the average film thickness of the antifouling layer 16 is as shown in the examples described later.
  • the antifouling layer 16 does not necessarily have to cover the entire surface of the silica-based porous film 14. For example, the surface of the silica-based porous film 14 may be partially covered, and the surface of the silica-based porous film 14 may be partially exposed.
  • the article 10 is, for example, a step of applying a silica-based porous film-forming coating solution on the transparent substrate 12 and firing to form a silica-based porous film 14 (hereinafter “first step”); A step of applying an antifouling layer-forming coating solution containing a plurality of nanosheets and a dispersion medium of the nanosheets on the surface of the silica-based porous membrane and drying to form an antifouling layer (hereinafter referred to as “second” It can be manufactured by performing the process ").”
  • the first step can be performed by a known production method according to the silica-based porous film to be formed, and is not particularly limited.
  • the first step is dispersed in the dispersion medium (a) and the dispersion medium (a).
  • a coating liquid hereinafter referred to as “topcoat liquid” containing fine particles (b) and a matrix precursor (c) dissolved or dispersed in the dispersion medium (a) is applied onto the transparent substrate 14 and baked.
  • topcoat liquid containing fine particles (b) and a matrix precursor (c) dissolved or dispersed in the dispersion medium (a) is applied onto the transparent substrate 14 and baked.
  • topcoat liquid containing fine particles (b) and a matrix precursor (c) dissolved or dispersed in the dispersion medium (a) is applied onto the transparent substrate 14 and baked.
  • topcoat liquid containing fine particles (b) and a matrix precursor (c) dissolved or dispersed in the dispersion medium (a) is applied onto the transparent substrate 14 and baked.
  • the dispersion medium (a) is a liquid that disperses the fine particles (b).
  • the dispersion medium (a) may be a solvent that dissolves the matrix precursor (c).
  • the matrix precursor (c) is a hydrolyzate of alkoxysilane, water is required for hydrolysis, and therefore it is preferable that the dispersion medium (a) contains at least water. Water and other liquids may be used in combination.
  • Examples of the other liquid include alcohols (methanol, ethanol, isopropanol, butanol, diacetone alcohol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.).
  • alcohols methanol, ethanol, isopropanol, butanol, diacetone alcohol, etc.
  • ketones acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
  • ethers tetrahydrofuran, 1,4-dioxane, etc.
  • Cellosolves methyl cellosolve, ethyl cellosolve, etc.
  • esters methyl acetate, ethyl acetate, etc.
  • glycol ethers ethylene glycol monoalkyl ether, etc.
  • nitrogen-containing compounds N, N-dimethylacetamide, N, N -Dimethylformamide, N-methylpyrrolidone, etc.
  • sulfur-containing compounds dimethylsulfoxide, etc.
  • solvent for the matrix precursor (c) alcohols are preferable, and methanol and ethanol are particularly preferable.
  • Examples of the fine particles (b) include metal oxide fine particles, metal fine particles, pigment-based fine particles, and resin fine particles.
  • the material of the metal oxide fine particles Al 2 O 3 , SiO 2 , SnO 2 , TiO 2 , ZrO 2 , ZnO, CeO 2 , Sb-containing SnO X (ATO), Sn-containing In 2 O 3 (ITO), RuO 2 and the like, from the viewpoint of low refractive index, SiO 2 is preferable.
  • Examples of the material of the metal fine particles include metals (Ag, Ru, etc.), alloys (AgPd, RuAu, etc.) and the like.
  • the pigment-based fine particles include inorganic pigments (titanium black, carbon black, etc.) and organic pigments.
  • the resin fine particle material include polystyrene and melanin resin.
  • Examples of the shape of the fine particles (b) include a spherical shape, an elliptical shape, a needle shape, a plate shape, a rod shape, a conical shape, a cylindrical shape, a cubic shape, a rectangular shape, a diamond shape, a star shape, and an indefinite shape.
  • the fine particles (b) may be hollow or perforated.
  • the fine particles (b) may be present in a state where each fine particle is independent, each fine particle may be linked in a chain shape, or each fine particle may be aggregated.
  • the fine particles (b) may be used alone or in combination of two or more.
  • the average aggregate particle diameter of the fine particles (b) is preferably 1 to 1,000 nm, more preferably 3 to 500 nm, and further preferably 5 to 300 nm. When the average aggregate particle diameter of the fine particles (b) is 1 nm or more, the antireflection effect is sufficiently high. If the average aggregate particle diameter of the fine particles (b) is 1,000 nm or less, the haze of the silica-based porous film 14 can be kept low.
  • the average aggregate particle diameter of the fine particles (b) is an average aggregate particle diameter of the fine particles (b) in the dispersion medium (a), and is measured by a dynamic light scattering method. In the case of monodispersed fine particles (b) in which no aggregation is observed, the average aggregate particle size is equal to the average primary particle size.
  • alkoxysilane examples include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.), alkoxysilane having a perfluoropolyether group (perfluoropolyether triethoxysilane, etc.), perfluoroalkyl.
  • Group alkoxysilane perfluoroethyltriethoxysilane, etc.
  • vinyl group alkoxysilane vinyltrimethoxysilane, vinyltriethoxysilane, etc.
  • epoxy group alkoxysilane (2- (3,4-epoxycyclohexyl), etc.
  • Alkoxysilanes (3-acryloyloxy propyl trimethoxysilane and the like) or the like having a Riroiruokishi group.
  • Hydrolysis of the alkoxysilane can be carried out in the same manner as the hydrolysis of the hydrolyzable silane compound.
  • a catalyst used at the time of hydrolysis a catalyst that does not disturb the dispersion of the fine particles (b) is preferable.
  • the topcoat liquid may contain a terpene derivative (d), other additives, and the like as necessary.
  • the terpene means a hydrocarbon having a composition of (C 5 H 8 ) n (where n is an integer of 1 or more) having isoprene (C 5 H 8 ) as a structural unit.
  • the terpene derivative means terpenes having a functional group derived from terpene.
  • the terpene derivative (d) includes those having different degrees of unsaturation.
  • terpene derivatives (d) function as a dispersion medium (a)
  • those that are “hydrocarbons having a composition of (C 5 H 8 ) n having isoprene as a structural unit” are terpene derivatives ( It corresponds to d), and shall not correspond to the dispersion medium (a).
  • the terpene derivative (d) is preferably a terpene derivative having a hydroxyl group and / or a carbonyl group in the molecule from the viewpoint of the antireflection effect of the silica-based porous film 14, and the hydroxyl group, aldehyde group (—CHO), A terpene derivative having at least one selected from the group consisting of a keto group (—C ( ⁇ O) —), an ester bond (—C ( ⁇ O) O—), and a carboxy group (—COOH) is more preferable. Further, a terpene derivative having at least one selected from the group consisting of a hydroxyl group, an aldehyde group, and a keto group is more preferable.
  • Terpene derivatives (d) include terpene alcohol ( ⁇ -terpineol, terpinene 4-ol, L-menthol, ( ⁇ ) citronellol, myrtenol, nerol, borneol, farnesol, phytol, etc.), terpene aldehyde (citral, ⁇ -cyclohexane). Citral, perilaldehyde, etc.), terpene ketones (( ⁇ ) camphor, ⁇ -ionone, etc.), terpene carboxylic acids (citronellic acid, abietic acid, etc.), terpene esters (terpinyl acetate, menthyl acetate, etc.) and the like. In particular, terpene alcohol is preferable.
  • a terpene derivative (d) may be used individually by 1 type, and may use 2 or more types together.
  • Examples of other additives include surfactants for improving leveling properties and metal compounds for improving durability of the silica-based porous film 14.
  • Examples of the surfactant include silicone oil and acrylic.
  • a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound and the like are preferable.
  • Examples of the zirconium chelate compound include zirconium tetraacetylacetonate and zirconium tributoxy systemate.
  • the viscosity of the top coat liquid is preferably 1.0 to 10.0 mPa ⁇ s, and more preferably 2.0 to 5.0 mPa ⁇ s. If the viscosity of the topcoat liquid is 1.0 mPa ⁇ s or more, it is easy to control the film thickness of the topcoat liquid applied on the transparent substrate 12. If the viscosity of the topcoat solution is 10.0 mPa ⁇ s or less, the drying or baking time and the coating time are shortened. The viscosity of the topcoat solution is measured with a B-type viscometer.
  • the solid content concentration of the top coat liquid is preferably 1 to 9% by mass, and more preferably 2 to 6% by mass. If the solid content concentration is 1% by mass or more, the film thickness of the top coat liquid applied on the transparent substrate 12 can be reduced, and the film thickness of the finally obtained silica-based porous film 14 is uniform. Easy to do. If solid content concentration is 9 mass% or less, it will be easy to make the film thickness of the coating film of the topcoat liquid apply
  • the solid content of the topcoat liquid means the sum of the fine particles (b) and the matrix precursor (c) (where the solid content of the matrix precursor (c) is the amount of alkoxysilane converted to SiO 2 ). .
  • the mass ratio (fine particles / matrix precursor) between the fine particles (b) and the matrix precursor (c) in the top coat solution is preferably 95/5 to 10/90, more preferably 70/30 to 90/10.
  • the fine particle / matrix precursor is 95/5 or less, the adhesion between the silica-based porous film 14 and the transparent substrate 12 is sufficiently high.
  • the fine particle / matrix precursor is 10/90 or more, the antireflection effect is sufficiently high.
  • the terpene derivative (d) is blended in the topcoat liquid, the blending amount is preferably 0.01 to 2 parts by weight, and 0.03 to 1 part by weight with respect to 1 part by weight of the solid content of the topcoat liquid. More preferred.
  • the antireflection effect is sufficiently high as compared with the case where the terpene derivative (d) is not added. If the terpene derivative (d) is 2 parts by mass or less, the strength of the silica-based porous film 14 will be good.
  • the top coat liquid is, for example, a mixture of a fine particle (b) dispersion, a matrix precursor (c) solution, and an additional dispersion medium (a), a terpene derivative (d), and other additives as necessary. It is prepared by.
  • the top coat liquid described above includes a dispersion medium (a), fine particles (b), and a matrix precursor (c), so that a silica-based porous film having an antireflection effect can be compared with a low cost at a low cost. It can be formed even at low temperatures. That is, when the silica-based porous film is formed using the above-described topcoat liquid, voids are selectively formed around the fine particles (b) in the silica-based porous film, and the voids have an antireflection effect. It has improved. Further, when the topcoat liquid contains the terpene derivative (d), the volume of the voids increases, and the antireflection effect is increased.
  • a method for applying the top coat liquid known wet coat methods (spin coat method, spray coat method, dip coat method, die coat method, curtain coat method, screen coat method, ink jet method, flow coat method, gravure coat method, bar (Coating method, flexo coating method, slit coating method, roll coating method, sponge roll coating method, squeegee coating method, etc.) can be used.
  • spin coat method spray coat method, dip coat method, die coat method, curtain coat method, screen coat method, ink jet method, flow coat method, gravure coat method, bar
  • the coating temperature is preferably room temperature to 80 ° C., more preferably room temperature to 60 ° C.
  • the coating of the topcoat liquid film formed on the transparent substrate may be performed after the topcoat liquid is applied.
  • the transparent substrate 12 is heated to a baking temperature in advance, and the surface of the transparent substrate 12 is heated. You may apply
  • the firing temperature is preferably 30 ° C. or higher, and may be appropriately determined according to the material of the transparent substrate 12, the fine particles (b), or the matrix precursor (c). In order to rapidly convert the hydrolyzate of alkoxysilane into a calcined product, it may be calcined at 80 ° C. or higher, preferably 100 ° C. or higher, and more preferably 200 to 700 ° C. When the firing temperature is 100 ° C. or higher, the fired product is densified and durability is improved.
  • the transparent base material 12 is glass
  • it can also serve as the baking process at the time of forming the silica type porous membrane 12, and the physical strengthening process of glass.
  • the glass is heated to near the softening temperature.
  • the firing temperature is set to about 600 to 700 ° C.
  • the firing temperature is preferably equal to or lower than the thermal deformation temperature of the transparent substrate 12.
  • the lower limit value of the firing temperature is determined according to the composition of the topcoat liquid. Since the polymerization proceeds to some extent even in natural drying, it is theoretically possible to set the drying or calcination temperature to a temperature setting near room temperature if there is no restriction on time.
  • an antifouling layer forming coating solution containing a plurality of nanosheets and a dispersion medium of the nanosheets on the surface of the silica-based porous film 14 formed on the surface of the transparent substrate 12 in the first step. (Hereinafter also referred to as “overcoat solution”) is applied and dried to form the antifouling layer 16. Thereby, the article 10 is obtained.
  • the overcoat liquid contains a plurality of nanosheets and a dispersion medium for the nanosheets.
  • nanosheet a layered product of a layered compound such as a commercially available layered polysilicate or layered clay mineral may be used, or one manufactured by a known manufacturing method may be used.
  • the nanosheet can be obtained, for example, by peeling off a layer constituting the natural or synthetic inorganic layered compound by a conventional method.
  • a nanosheet dispersion liquid in which nanosheets are dispersed in water can be obtained by adding an inorganic layered compound to water to swell and stirring.
  • an inorganic layered compound in order to improve the dispersibility to a solvent, you may use what processed the surface and the interlayer previously with surfactant etc.
  • the nanosheet dispersion liquid can be used as it is as an overcoat liquid or for the preparation of an overcoat liquid.
  • an overcoat liquid can be prepared by mixing a nanosheet dispersion and a solution of an optional component (such as a binder or a precursor thereof).
  • the content of the nanosheet in the overcoat liquid is not particularly limited as long as the overcoat liquid can be applied, but is 0.05 to 0.50 mass% with respect to the total amount of the overcoat liquid (100 mass%). Is preferable, and 0.10 to 0.35 mass% is more preferable. If the content of the nanosheet is 0.05% by mass or more, an arbitrary component dissolved in the overcoat liquid is less likely to penetrate into the silica-based porous film 14 when the overcoat liquid is applied. If the content of the nanosheet is 0.50% by mass or less, the coating property of the overcoat liquid is good, a thin antifouling layer can be formed, and the uniformity of the film thickness of the antifouling layer to be formed is also good. .
  • the dispersion medium is a liquid that disperses the nanosheet.
  • the dispersion medium is preferably a solvent that dissolves the binder.
  • the dispersion medium may be a single liquid or a mixed liquid obtained by mixing two or more liquids.
  • water is preferably used. You may use water and an organic solvent together as needed.
  • an organic solvent may be used alone.
  • organic solvent examples include alcohols (methanol, ethanol, isopropanol, butanol, diacetone alcohol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), Cellosolves (methyl cellosolve, ethyl cellosolve, etc.), esters (methyl acetate, ethyl acetate, etc.), glycol ethers (ethylene glycol monoalkyl ether, etc.), nitrogen-containing compounds (N, N-dimethylacetamide, N, N-dimethyl) Formamide, N-methylpyrrolidone, etc.), sulfur-containing compounds (dimethyl sulfoxide, etc.) and the like.
  • alcohols methanol, ethanol, isopropanol, butanol, diacetone alcohol, etc.
  • ketones acetone, methyl
  • the content of water in the overcoat liquid is preferably 60% by mass or less, and more preferably 50% by mass or less with respect to the total mass of the overcoat liquid.
  • the content of water in the overcoat liquid is more than 60% by mass, the solvent is not sufficiently dried in the drying step after coating, and the appearance of the coating film is liable to occur.
  • a binder or a precursor thereof is blended in the overcoat liquid.
  • a binder precursor is blended in the overcoat liquid.
  • the binder precursor may be a hydrolyzate of a hydrolyzable silane compound or a hydrolyzable silane compound that is a precursor thereof. The description of the binder and its precursor is the same as described above.
  • the content is such that the mass ratio of the nanosheet content to the total amount of the nanosheet and the binder or its precursor (nanosheet / (nanosheet + binder)) is 0.25 or more. Is preferred.
  • the value of nanosheet / (nanosheet + binder) is more preferably 0.375 or more, and particularly preferably 0.50 or more.
  • the nanosheet / (nanosheet + binder) is 0.25 or more, the decrease in the antireflection performance of the silica-based porous film 14 due to the penetration of the binder is suppressed, and the maximum transmittance by providing the antifouling layer 16 is reduced. The decrease can be sufficiently suppressed.
  • the total amount of the nanosheet and the binder or precursor thereof is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, based on the total mass of the solid content in the overcoat liquid.
  • the binder is a hydrolyzate of a hydrolyzable silane compound
  • the content of the binder or its precursor is in terms of SiO 2 solids.
  • the overcoat liquid is prepared, for example, by mixing the nanosheet dispersion and the binder or its precursor solution.
  • a surfactant is preferable.
  • the compounding amount of the surfactant is preferably such that the mass ratio of the surfactant content to the nanosheet content (surfactant / nanosheet) is 1.5 or less.
  • the transmittance tends to decrease due to the penetration of the surfactant component into the porous silica membrane.
  • the solid content concentration in the overcoat liquid is preferably 0.05 to 0.50 mass%, more preferably 0.1 to 0.4 mass%. If the solid content concentration in the overcoat liquid is less than 0.05% by mass, the antifouling property tends to be insufficient. On the other hand, if it exceeds 0.50% by mass, the antifouling layer becomes too thick and the transmittance tends to be insufficient.
  • the overcoat liquid As a method for applying the overcoat liquid, known wet coat methods (spin coat method, spray coat method, dip coat method, die coat method, curtain coat method, screen coat method, ink jet method, flow coat method, gravure coat method, bar (Coating method, flexo coating method, slit coating method, roll coating method, sponge roll coating method, squeegee coating method, etc.) can be used.
  • the coating temperature is preferably room temperature to 80 ° C, more preferably 35 to 60 ° C.
  • An antifouling layer-forming coating solution is applied to the surface of the silica-based porous film, and after forming a coating film, the antifouling layer 16 is formed by drying or the like.
  • the overcoat liquid contains only the nanosheet as a solid content, that is, when it does not contain any optional component other than the nanosheet (binder or precursor thereof, surfactant, etc.)
  • drying after coating only needs to be able to remove the dispersion medium.
  • the drying conditions are not particularly limited, but preferably satisfy the following drying conditions 1. (Drying condition 1) The drying is performed at a drying temperature of 300 ° C. or lower (more preferably 250 ° C. or lower, more preferably 200 ° C. or lower).
  • the lower limit of the drying temperature is not particularly limited, but the substrate temperature is preferably 60 ° C. or higher, and more preferably 80 ° C. or higher. If it is 60 degreeC or more, a dispersion medium will fully be removed.
  • drying after coating is preferably performed at a temperature that satisfies the above-described drying condition 1 and does not exceed the thermal decomposition temperature of the binder.
  • the binder in the antifouling layer is thermally decomposed, and the effect of including the binder (for example, improved adhesion between nanosheets in the antifouling layer, improved denseness of the antifouling layer, etc. ) May be damaged.
  • the lower limit of the drying temperature is not particularly limited, but the substrate temperature is preferably 60 ° C. or higher and more preferably 80 ° C. If it is 60 degreeC or more, a dispersion medium will fully be removed.
  • the overcoat liquid contains an organic substance other than the binder and its precursor, for example, a surfactant, etc.
  • drying after coating is performed at a temperature that satisfies the above-mentioned drying condition 1 and does not exceed the thermal decomposition temperature of the organic substance. It is preferable to perform drying.
  • the organic substance When heated to a temperature equal to or higher than the thermal decomposition temperature, the organic substance may be thermally decomposed and the effects of inclusion may be impaired.
  • the lower limit of the drying temperature is not particularly limited, but the substrate temperature is preferably 60 ° C. or higher, and more preferably 80 ° C. If it is 60 degreeC or more, a dispersion medium will fully be removed.
  • the thermal decomposition temperature of the organic substance can be measured by differential thermal-thermogravimetric simultaneous measurement (TG-DTA).
  • the antifouling antireflection film of the present invention has an antifouling layer on the surface of the silica-based porous film, so that the antifouling property is enhanced while maintaining the antireflection performance of the silica-based porous film. Therefore, the article of the present invention having the antifouling antireflection film of the present invention on the surface of the transparent substrate has a maximum transmittance higher than that of the transparent substrate and also has a good antifouling property.
  • Articles of the present invention include vehicle transparent parts (headlight covers, side mirrors, front transparent substrates, side transparent substrates, rear transparent substrates, instrument panels, etc.), meters, architectural windows, show windows, displays (notebook computers) , Monitor, LCD, PDP, ELD, CRT, PDA, etc.), LCD color filter, touch panel substrate, pickup lens, optical lens, spectacle lens, camera component, video component, CCD cover substrate, optical fiber end surface, projector component, copy Machine parts, transparent substrates for solar cells, mobile phone windows, backlight unit parts (for example, light guide plates, cold cathode tubes, etc.), backlight unit parts (for example, prisms, transflective films, etc.), liquid crystal brightness enhancement films, organic EL light-emitting element parts, inorganic EL light-emitting element parts It is useful as a phosphor light emitting element part, an optical filter, an end face of an optical part, an illumination lamp, a cover for a lighting fixture, an amplification laser light source, an antireflection film,
  • examples 1 to 29 are examples, and examples 22 to 29 are comparative examples.
  • the measurement method, evaluation method, and raw materials (nanosheet dispersion and other raw materials) used in each example are shown below.
  • Nanosheet refractive index The film-coated substrate obtained by applying the nanosheet dispersion on the silicon substrate was measured with an ellipsometer (JA Woollam, model: M-2000DI), and the refractive index of the nanosheet at a wavelength of 589 nm was determined.
  • the average thickness of the nanosheet was calculated as follows.
  • the nanosheet dispersion was applied onto a glass substrate by spin coating, the surface was observed with an atomic force microscope (manufactured by SII Nanotechnology), and the average value of 10 nanosheets arbitrarily selected from a measurement range of 2 ⁇ m square was used as the average thickness.
  • the average width of the nanosheet was calculated as follows. Observed with the atomic force microscope, the length of the line segment connecting the two most distant points on one nanosheet was determined. The length of the longest line segment was calculated
  • the average value of these two line segments was taken as the width of the nanosheet, this operation was performed on any 10 nanosheets, and the average value of the 10 widths was taken as the average width.
  • the average area was calculated as follows. The product of two line segments calculated in the same manner as described above for one nanosheet was obtained, and the value divided by 2 was defined as the area of the nanosheet. This operation was performed on any 10 nanosheets, and the average value of the 10 areas was defined as the average area.
  • the wavelength at which the maximum transmittance can be obtained in the measurement of the maximum transmittance (0 ° incidence) is compared before and after applying the overcoat liquid (that is, the coating liquid for forming the antifouling layer), and the antifouling formed.
  • the layer thickness was calculated.
  • Maximum transmittance change by application Maximum transmittance of transparent base material with silica-based porous film before forming antifouling layer (hereinafter referred to as “maximum transmittance before application”), maximum transmittance of articles obtained by forming antifouling layer (hereinafter referred to as “maximum after application”) “Transmittance”) was measured in the same manner as described above, and the amount of change in each maximum transmittance (maximum transmittance (%) after coating ⁇ maximum transmittance (%) before coating) was calculated.
  • the amount of change is preferably within the range of -0.2 to 0.2, and particularly preferably within the range of -0.1 to 0.2.
  • peel strength test As an index of antifouling properties, the peel strength of an ethylene-vinyl acetate copolymer resin (EVA) film was measured by the following procedure. An EVA film having a thickness of 0.8 mm was cut into a width of 5 mm and a length of 80 mm, placed on the surface of the antifouling layer side of the article obtained in each example, and held in a drying furnace at 160 ° C. for 30 minutes. After removing from the drying oven and the substrate temperature has dropped to room temperature, the force necessary to peel off the EVA film adhering to the antifouling layer (hereinafter referred to as “peeling force”, unit: g / 5 mm) And measured. It shows that an EVA film is easy to peel, that is, it is excellent in antifouling property, so that this peeling force is small.
  • peeling force unit: g / 5 mm
  • the removability of the antifouling layer during outdoor exposure was evaluated by the following procedure.
  • the antifouling low-reflection films of Examples 2, 7, 10, 21, and 29 described later were left outdoors.
  • the maximum transmittance of the article was measured as described above.
  • the removal performance of the antifouling layer was evaluated by comparing the maximum transmittance before and after exposure. As the maximum transmittance after exposure is closer to the maximum transmittance before formation of the antifouling layer, the removability of the antifouling layer is higher than the maximum transmittance before exposure.
  • Chain-like SiO 2 fine particle dispersion (b1) “Snowtex (trade name) OUP” manufactured by Nissan Chemical Industries, Ltd., solid content concentration of 15.5% by mass in terms of SiO 2 , average primary particle size of 10 to 20 nm, and average aggregated particle size of 40 to 100 nm.
  • Preparation of matrix precursor solution (c1) While stirring 77.6 g of denatured ethanol (manufactured by Nippon Alcohol Sales Co., Ltd., Solmix AP-11 (trade name), a mixed solvent containing ethanol as a main ingredient, the same applies hereinafter), 11.9 g and 61 of ion-exchanged water were added thereto. A mixed solution of 0.1% by mass of nitric acid was added and stirred for 5 minutes. To this, 10.4 g of tetraethoxysilane (SiO 2 equivalent solid content concentration: 29% by mass) is added and stirred at room temperature for 30 minutes, and the matrix precursor solution having a SiO 2 equivalent solid content concentration of 3.0% by mass ( c1) was prepared.
  • SiO 2 in terms of solid concentration is a solid content concentration when all Si of tetraethoxysilane was converted to SiO 2.
  • nanosheet dispersion (B) Synthetic smectite (“Lucentite SWN” manufactured by Coop Chemical Co., Ltd.) was chemically modified by the method described in JP-A-6-2870146, and a nanosheet dispersion liquid (B) in which this was dispersed was prepared. Specifically, a suspension was prepared by dispersing 2 g of synthetic smectite (“Lucentite SWN” manufactured by Coop Chemical Co., Ltd.) in 100 mL of distilled water.
  • An aqueous colloidal titanate sheet was prepared as follows. A mixture of the stoichiometric composition of Cs 2 CO 3 and TiO 2 was calcined at 800 ° C. for 20 hours to prepare a cesium titanate precursor. 70 g of the obtained cesium titanate precursor was immersed in 2 L of a 1 mol / L HCl solution. The acid treatment with the HCl solution was performed a total of 3 times by exchanging with a new solution every 24 hours. The obtained acid substitution product was filtered, washed with water, and dried in the air.
  • the obtained proton titanate was added to a 0.0017 mol / L tetrabutylammonium hydroxide solution and shaken vigorously at room temperature for 10 days to obtain a milky white colloidal suspension.
  • a milky white colloidal suspension By concentrating the obtained liquid, it adjusted to solid content 0.4 mass%, and obtained the nanosheet dispersion liquid (D).
  • the composition of the prepared nanosheet dispersion is shown in Table 1.
  • SWN indicates “Lucentite SWN” manufactured by Corp Chemical.
  • SWN is a powdered smectite.
  • the form thereof was a sheet (nanosheet).
  • the refractive index, average thickness, average width, and average area of each nanosheet were measured, the results shown in Table 1 were obtained.
  • binder solution (G) silane hydrolysis sol: While stirring 80.5 g of denatured ethanol, a mixture of 11.4 g of ion-exchanged water and 0.5 g of 10% by mass nitric acid was added thereto and stirred for 5 minutes. To this, 7.6 g of tetraethoxysilane (SiO 2 equivalent solid content concentration: 29% by mass) was added and stirred at room temperature for 30 minutes, and a sol having a SiO 2 equivalent solid content concentration of 2.2% by mass (binder solution ( G)) was prepared.
  • SiO 2 equivalent solid content concentration 29% by mass
  • Example 1 An article having the same layer structure as that of the article 10 shown in FIG. 1 was produced by the following procedure. An undercoat layer was provided on the surface of the template glass, and this was used as the transparent substrate 12.
  • Template glass made by Asahi Glass Co., Ltd., Solite (trade name), low iron soda lime glass (white plate glass) with a satin pattern formed on it. Size: 100 mm x 100 mm, thickness: 3.2 mm) Prepared, the surface of the flat surface of the template glass was polished with an aqueous cerium oxide dispersion, rinsed with cerium oxide with water, rinsed with ion-exchanged water, and dried.
  • top coat The template glass on which the undercoat was formed as described above was preheated in a preheating furnace (manufactured by ISUZU, VTR-115), and the surface temperature was kept at 30 ° C., the reverse roll coater (Sanwa) The topcoat solution (a1) was applied with a coating roll manufactured by Seiki Co., Ltd. Then, it baked for 30 minutes at 500 degreeC in air
  • Examples 2 to 17 Except for changing the composition of the overcoat solution, articles were obtained by carrying out glass washing, undercoat, topcoat and overcoat in exactly the same manner as in Example 1.
  • the overcoat solution used in each example was prepared by the following procedure. Tables 2 to 3 show the raw materials and blending amounts used for the preparation in each example. Application and drying of these overcoat solutions were performed in the same manner as in Example 1.
  • the overcoat liquid used in Example 2 was prepared by adding 35 g of the nanosheet dispersion (A) to 15 g of distilled water, stirring 50 g of ethanol, and stirring for 10 minutes.
  • the overcoat liquid used in Example 3 was prepared by adding 50 g of ethanol thereto and stirring for 10 minutes while stirring 50 g of the nanosheet dispersion liquid (A).
  • the overcoat solution used in Example 4 was prepared by adding 1.92 g of nanosheet dispersion (B) to 98.08 g of ethanol and stirring for 10 minutes.
  • the overcoat solution used in Example 5 was prepared by adding 3.85 g of nanosheet dispersion liquid (B) to 96.15 g of ethanol and stirring for 10 minutes.
  • the overcoat solution used in Example 6 was prepared by adding 5.77 g of nanosheet dispersion liquid (B) to 94.23 g of ethanol and stirring for 10 minutes.
  • the overcoat liquid used in Example 7 was prepared by adding 9.62 g of nanosheet dispersion liquid (B) to 90.38 g of ethanol and stirring for 10 minutes.
  • the overcoat liquid used in Example 8 was prepared by adding 19.2 g of nanosheet dispersion (B) to 80.8 g of ethanol and stirring for 10 minutes.
  • the overcoat liquid used in Example 9 was added with 25 g of nanosheet dispersion (A) while stirring 24 g of water, further added with 1 g of binder solution (E), and finally added 50 g of ethanol and stirred for 10 minutes.
  • the overcoat liquid used in Example 10 was stirred with 20 g of water while adding 25 g of the nanosheet dispersion (A), further adding 5 g of the binder solution (E), and finally adding 50 g of ethanol and stirring for 10 minutes.
  • the overcoat liquid used in Example 11 was added with 25 g of nanosheet dispersion (A) while stirring 15 g of water, added with 10 g of binder solution (E), and finally added 50 g of ethanol and stirred for 10 minutes.
  • Example 9 The overcoat liquid used in Example 9 was added with 25 g of nanosheet dispersion (A) while stirring 24 g of water, further added with 1 g of binder solution (E), and finally added 50 g of ethanol and stirred for 10 minutes.
  • the overcoat liquid used in Example 12 was stirred with 10 g of water, 25 g of nanosheet dispersion (A) was added thereto, 15 g of binder solution (E) was further added, and 50 g of ethanol was finally added, followed by stirring for 10 minutes.
  • the overcoat liquid used in Example 13 was stirred with 10 g of water, 20 g of nanosheet dispersion (A) was added thereto, 20 g of binder solution (E) was further added, and 50 g of ethanol was finally added, followed by stirring for 10 minutes.
  • the overcoat liquid used in Example 13 was stirred with 10 g of water, 20 g of nanosheet dispersion (A) was added thereto, 20 g of binder solution (E) was further added, and 50 g of ethanol was finally added, followed by stirring for 10 minutes.
  • Example 12 was stirred with 10 g of water, 25 g of nanosheet dispersion (A) was added thereto, 15 g of binder solution (E) was further added, and 50 g
  • the overcoat liquid used in Example 14 was stirred with 10 g of water, 15 g of nanosheet dispersion (A) was added thereto, 25 g of binder solution (E) was further added, and 50 g of ethanol was finally added, followed by stirring for 10 minutes.
  • the overcoat liquid used in Example 15 was stirred with 10 g of water while adding 10 g of the nanosheet dispersion (A), further adding 30 g of the binder solution (E), and finally adding 50 g of ethanol and stirring for 10 minutes.
  • the overcoat liquid used in Example 15 was stirred with 10 g of water while adding 10 g of the nanosheet dispersion (A), further adding 30 g of the binder solution (E), and finally adding 50 g of ethanol and stirring for 10 minutes.
  • overcoat liquid used in Example 16 25 g of nanosheet dispersion (A) was added thereto while stirring 25 g of water, 42.5 g of ethanol was further added, and 7.5 g of binder solution (F) was finally added. Prepared by stirring for 10 minutes.
  • the overcoat liquid used in Example 17 was stirred with 50.4 g of ethanol, 9.6 g of nanosheet dispersion liquid (B) was added thereto, further 25 g of water was added, and finally 15 g of binder solution (E) was added. It was prepared with.
  • Example 18 The overcoat solution used in Example 18 was stirred with 72.9 g of ethanol, 9.6 g of nanosheet dispersion (B) was added thereto, 7.5 g of binder solution (F) was added, and finally 10 g of water was added. In addition, it was prepared by stirring for 10 minutes.
  • Example 19 to 20 Articles were obtained by performing glass washing, undercoat, topcoat, and overcoat in exactly the same manner as in Example 1 except that the drying conditions after application of the overcoat solution were changed.
  • the composition of the overcoat solution and the coating method are the same as in Example 1. In Example 19, drying after applying the overcoat solution was performed at 300 ° C. for 1 minute, and in Example 20, it was performed at 400 ° C. for 1 minute.
  • Example 21 Articles were obtained by performing glass washing, undercoat, topcoat, and overcoat in exactly the same manner as in Example 1 except that the nanosheet dispersion liquid (C) was used as it was as an overcoat liquid.
  • the composition, coating and drying of the overcoat solution are the same as in Example 1.
  • Example 22 Only the glass washing, undercoat, and topcoat were performed in the same manner as in Example 1 to obtain a transparent substrate with a silica-based porous film. Subsequent overcoating was not performed, and the substrate with the silica-based porous film was used as the article of Example 22.
  • Example 23 to 29 Except for changing the composition of the overcoat solution, articles were obtained by carrying out glass washing, undercoat, topcoat and overcoat in exactly the same manner as in Example 1.
  • the overcoat solution used in each example was prepared by the following procedure. Table 4 shows the raw materials and blending amounts used for the preparation in each example. Application and drying of these overcoat solutions were performed in the same manner as in Example 1.
  • the overcoat liquid used in Example 23 was prepared by adding 50 g of ethanol thereto and stirring for 10 minutes while stirring 50 g of the nanosheet dispersion liquid (A ′).
  • the overcoat liquid used in Example 24 was prepared by adding 0.96 g of the nanosheet dispersion liquid (B) and stirring for 10 minutes while stirring 99.04 g of ethanol.
  • the overcoat liquid used in Example 25 was prepared by adding 15 g of the binder solution (E) thereto while stirring 35 g of water, and finally adding 50 g of ethanol and stirring for 10 minutes.
  • the overcoat solution used in Example 26 was prepared by adding 40 g of the binder solution (E) to 10 g of water while stirring, and finally adding 50 g of ethanol and stirring for 10 minutes.
  • the overcoat solution used in Example 27 was prepared by adding 40 g of the binder solution (G) thereto while stirring 60 g of ethanol and stirring the mixture for 10 minutes.
  • the overcoat solution used in Example 28 was prepared by adding 7.5 g of a surfactant solution (H) to 92.5 g of ethanol and stirring for 10 minutes.
  • the nanosheet dispersion liquid (D) was used as it was as an overcoat liquid.
  • Example 2 the SEM photograph of the outermost surface by the side of the silica type porous membrane of the transparent base material with a silica type porous membrane before forming an antifouling layer is shown in FIG. The outermost surface on the side is shown in FIG. 3A, and the cross section is shown in FIG.
  • the peel strength in the resin peel strength test is 740 g / 5 mm or less, and the peel strength (840 g / 5 mm) in the transparent substrate with a silica-based porous film (Example 22) before forming the antifouling layer ) Is smaller than 100 g / 5 mm. From this, it was confirmed that the antifouling property was imparted by forming the antifouling layer.
  • the maximum transmittance change amount by applying the overcoat liquid is ⁇ 0.16 to 0.13, and the antireflection performance does not decrease or decreases even when the antifouling layer is formed. It was also confirmed that it was slight.
  • Example 23 in which the film thickness of the formed antifouling layer was 41 nm was lowered.
  • Example 24 in which the film thickness of the antifouling layer was less than 0.4 nm, the effect of imparting antifouling properties was small, and the peeling force was large (780 g / 5 mm).
  • Example 25 in which the binder was used alone as the solid content of the overcoat liquid and the solid content concentration was 0.15%, the effect of imparting antifouling properties was small, and the peel force was as large as 760 g / 5 mm.
  • Example 26 In Examples 26 and 27 in which the solid content concentration was increased to 0.40% with the binder alone, the antireflection performance was lowered. In Example 28 in which the surfactant was used alone as the solid content of the overcoat liquid, the effect of imparting antifouling properties was small, and the antireflection performance was also lowered. In Example 29 using the titanium oxide nanosheet, the maximum transmittance decreased by 0.55% due to the high refractive index of the antifouling layer.
  • the antifouling antireflection film capable of maintaining a good appearance over a long period of time while improving the antifouling property while maintaining the antireflection performance of the silica-based porous film, and the antifouling antireflection film are provided.
  • Articles and methods for producing the same can be provided, and are useful as cover members for solar cells, various displays and their front plates, various window glasses, touch panel cover members, and the like.

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Abstract

L'invention concerne : un film antireflet antisalissure qui présente des propriétés antisalissure améliorées, qui préserve les performances antireflet d'un film de silice poreux, et qui peut conserver un bel aspect pendant longtemps ; un article qui est muni du film antireflet antisalissure ; ainsi qu'un procédé de fabrication de ce film et de cet article. Ledit film antireflet antisalissure comprend un film de silice poreux ainsi qu'une couche antisalissure qui recouvre la surface du film de silice poreux, cette couche antisalissure comportant une pluralité de nanofeuilles, les nanofeuilles étant constituées d'un matériau à faible réfraction dont l'indice de réfraction est de 1,4 à 1,65, et l'épaisseur de film moyenne de la couche antisalissure étant de 0,4 à 40 nm.
PCT/JP2013/077817 2012-10-15 2013-10-11 Film antireflet antisalissure, article, et procédé de fabrication de ce film et de cet article WO2014061606A1 (fr)

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WO2015155830A1 (fr) * 2014-04-08 2015-10-15 日産自動車株式会社 Structure antiencrassement de durabilité élevée et pièce d'automobile l'utilisant
WO2017216592A3 (fr) * 2016-06-15 2018-03-15 Hungaro Lux Light Kft Film antireflet et son utilisation sur un substrat
CN111253782A (zh) * 2020-02-12 2020-06-09 首钢集团有限公司 改性防腐水滑石、水性智能防腐涂料、制备方法及涂层
WO2020153352A1 (fr) 2019-01-21 2020-07-30 公立大学法人大阪 Dispersion liquide de couche exfoliée de composé multicouche, et substrat transparent l'utilisant
CN113289413A (zh) * 2021-05-25 2021-08-24 九江市磐泰复合材料有限公司 一种高容量氟玻璃纤维过滤材料的制备方法
EP3692104A4 (fr) * 2017-10-03 2021-09-01 Massachusetts Institute of Technology Matériaux qui résistent à l'encrassement et procédés pour leur identification
WO2022181628A1 (fr) 2021-02-24 2022-09-01 国立大学法人熊本大学 Dispersion de particules exfoliées d'un composé polysilicate stratifié, et son procédé de production

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CN106277839B (zh) * 2015-05-15 2018-10-30 中国科学院理化技术研究所 一种具有超双疏自清洁及减反增透性能的复合薄膜及其制备方法
JP7091315B2 (ja) * 2017-04-14 2022-06-27 Hoya株式会社 光学素子及びその製造方法
JP7218539B2 (ja) * 2018-10-19 2023-02-07 三菱ケミカル株式会社 表面被覆層形成用塗工液及び多孔質ケイ素積層体
WO2023140194A1 (fr) * 2022-01-20 2023-07-27 日東電工株式会社 Élément optique, son procédé de production et élément optique

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Publication number Priority date Publication date Assignee Title
WO2015155830A1 (fr) * 2014-04-08 2015-10-15 日産自動車株式会社 Structure antiencrassement de durabilité élevée et pièce d'automobile l'utilisant
WO2017216592A3 (fr) * 2016-06-15 2018-03-15 Hungaro Lux Light Kft Film antireflet et son utilisation sur un substrat
US20190177553A1 (en) * 2016-06-15 2019-06-13 Hungaro Lux Light Kft. Antireflection Film and Its Use on a Substrate
US11029514B2 (en) 2016-06-15 2021-06-08 Hungaro Lux Light Kft. Antireflection film and its use on a substrate
EP3692104A4 (fr) * 2017-10-03 2021-09-01 Massachusetts Institute of Technology Matériaux qui résistent à l'encrassement et procédés pour leur identification
US11267972B2 (en) 2017-10-03 2022-03-08 Massachusetts Institute Of Technology Materials that resist fouling and methods for identifying same
WO2020153352A1 (fr) 2019-01-21 2020-07-30 公立大学法人大阪 Dispersion liquide de couche exfoliée de composé multicouche, et substrat transparent l'utilisant
KR20210123325A (ko) 2019-01-21 2021-10-13 닛산 가가쿠 가부시키가이샤 층상 화합물의 박리층 분산액 및 그것을 이용한 투명기판
CN111253782A (zh) * 2020-02-12 2020-06-09 首钢集团有限公司 改性防腐水滑石、水性智能防腐涂料、制备方法及涂层
WO2022181628A1 (fr) 2021-02-24 2022-09-01 国立大学法人熊本大学 Dispersion de particules exfoliées d'un composé polysilicate stratifié, et son procédé de production
KR20230147206A (ko) 2021-02-24 2023-10-20 고꾸리쯔다이가꾸호오진 구마모또 다이가꾸 층상 폴리규산염 화합물의 박리입자 분산액, 및 그의 제조방법
CN113289413A (zh) * 2021-05-25 2021-08-24 九江市磐泰复合材料有限公司 一种高容量氟玻璃纤维过滤材料的制备方法

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