US20050008876A1 - Ultra-water-repellent substrate - Google Patents

Ultra-water-repellent substrate Download PDF

Info

Publication number
US20050008876A1
US20050008876A1 US10/494,867 US49486704A US2005008876A1 US 20050008876 A1 US20050008876 A1 US 20050008876A1 US 49486704 A US49486704 A US 49486704A US 2005008876 A1 US2005008876 A1 US 2005008876A1
Authority
US
United States
Prior art keywords
film
projections
hydrophobic
substrate
super
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US10/494,867
Other languages
English (en)
Inventor
Toyoyuki Teranishi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Sheet Glass Co Ltd
Original Assignee
Individual
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 Individual filed Critical Individual
Assigned to NIPPON SHEET GLASS COMPANY, LIMITED reassignment NIPPON SHEET GLASS COMPANY, LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TERANISHI, TOYOYUKI
Publication of US20050008876A1 publication Critical patent/US20050008876A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/1033—Laminated safety glass or glazing containing temporary protective coatings or layers
    • 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
    • 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
    • C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
    • 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
    • C03C2217/76—Hydrophobic and oleophobic coatings
    • 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
    • C03C2217/77—Coatings having a rough surface
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/114—Deposition methods from solutions or suspensions by brushing, pouring or doctorblading
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12389—All metal or with adjacent metals having variation in thickness
    • Y10T428/12396—Discontinuous surface component
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31—Surface property or characteristic of web, sheet or block

Definitions

  • the present invention relates to super-hydrophobic substrates that are useful for, for example, glass sheets for vehicles.
  • the surface may be provided with minute recesses and projections.
  • the wettability of solid surfaces depends on the roughness of the surface. That is to say, if the solid surface is hydrophilic, then a rough surface increases its hydrophilicity, and if the solid surface is hydrophobic, then a rough surface increases its hydrophobicity. This phenomenon is particularly pronounced when the surface has a fractal structure, and as a result, fractal surfaces may be so-called super-hydrophobic or super-hydrophilic surfaces, depending on the material of the fractal surface.
  • hydrophobic state in which the contact angle of water is greater than 150° is generally referred to as “super-hydrophobic.”
  • JP 6(1994)-25449 A discloses a method in which the surface of a plastic film is provided with fine protrusions by plasma processing, and then a fluorine compound is chemisorbed.
  • JP 11(1999)-286784 A discloses a method of forming a finely textured structure on a glass surface by applying a processing solution including a polycondensate of a metal alkoxide, metal oxide particles, and a silane compound having a fluoroalkyl group, and then drying the processing solution.
  • JP 2000-144116 A discloses a hydrophobic film providing a surface with recesses and projections by applying to a substrate an application solution including a polycondensate of trialkoxylsilane, and thermally processing it.
  • JP 2001-17907 A discloses a method of providing a surface with a fine texture by forming a coating on a substrate by applying a solution including an aluminum compound, and immersing it in warm water.
  • JP 2001-207123 A discloses a method of forming a layer with micropores of 100 nm to 2 ⁇ m average pore diameter by applying to a substrate a solution obtained by adding to a solvent metal alkoxides and a substance having the property of phase splitting with these in the solvent and decomposing, combusting or sublimating at temperatures between room temperature and 700° C., followed by thermal processing.
  • the thickness and/or the texture of the film is large. Therefore, transmitted light is scattered, and the haze value increases, so that there is the disadvantage that the transparency of the film is low.
  • the texture is formed by plasma processing, so that it requires equipment for plasma processing.
  • the texture is formed by immersion in warm water, so that it necessitates equipment for supplying warm water.
  • drying is performed after forming a wet coating film by dip coating, so that irregularities easily appear on the glass edges and the film surface, deteriorating the appearance of the coating.
  • the texture of the film surface has an irregular fractal structure, so that the abrasion resistance of the film becomes poor.
  • the contact angle exceeds 150° a super-hydrophobic surface is attained, on which water droplets hardly stay still. It is said that in order to realize such a super-hydrophobic surface, a shape is necessary in which a lot of air is kept between the surface texture and the water drops.
  • the present invention provides a super-hydrophobic substrate that includes a substrate; an undercoating film formed on the substrate in which minute recesses and protrusions are formed in its surface; and a hydrophobic film formed on the minute recesses and protrusions of the undercoating film.
  • the surface shape of the hydrophobic film reflects the minute recesses and protrusions, and a contact angle CA and a tumbling angle TA of a water droplet on the surface of the hydrophobic film satisfy the following relationships.
  • FIG. 1 is a diagram showing a relationship between the contact angle and the tumbling angle.
  • FIG. 2A to FIG. 2D are schematic views describing the mechanism through which the minute recesses and projections are formed.
  • FIG. 3 is a diagram showing a glass sheet coated with a hydrophobic film obtained in Example 1 as observed by a scanning electron microscope (SEM).
  • FIG. 4 is a diagram showing a glass sheet coated with a hydrophobic film obtained in Example 5 as observed by a SEM.
  • the CA and TA satisfy: CA ⁇ 150° and TA ⁇ 7°.
  • the undercoating film preferably contains silicon oxide as its main component.
  • the surface shape of the hydrophobic film is composed of granular projections and columnar projections that are higher than the granular projections when measured from the surface of the substrate.
  • Dc is the diameter of the columnar projections and H is their height
  • Dc and H preferably satisfy: 2Dc ⁇ H, more preferably 3Dc ⁇ H.
  • a surface roughness of the hydrophobic film expressed as an arithmetic mean roughness value (Ra) is 10 nm or more, and a haze value (ratio) of the film is 1% or less.
  • Ra arithmetic mean roughness value
  • ratio a haze value of the film
  • the hydrophobic film may be, for example, a fluoroalkyl group-containing organic film.
  • the substrate various materials such as glass, resin and metal can be used, and the substrate may be a laminated glass or a tempered glass. These glass sheets can be used for vehicles, for example, a laminated glass is used as a windshield. Since the hydrophobic film of the present invention can be formed without sintering, the film is suitable for a processed glass such as a laminated glass.
  • the relationship between the contact angle and the tumbling angle is restricted.
  • the inventor manufactured windshields having various combinations between contact angles and tumbling angles by the same method as in the present invention, and conducted visual sensory testing by four people of Mr. A, Mr. B, Mr. C, and Mr. D. This testing was based on visibility of the windshields on which water droplets were scattered.
  • the range of 145° or more in contact angle and the range of 15° or less in tumbling angle can be regarded as a good visibility region, and the range of more than 5° in tumbling angle may be regarded as a poor visibility region.
  • the range of 150°> contact angle (CA) ⁇ 145° and tumbling angle (TA) ⁇ 5° also can provide good visibility.
  • Such a super-hydrophobic substrate can be obtained by forming a hydrophobic film containing fluoroalkyl groups on minute recesses and projections that are formed on a substrate surface.
  • the contact angle is determined by measuring a contact angle of a 4 ⁇ L water droplet on a horizontal surface.
  • the tumbling angle is determined by measuring a critical angle of a 50 ⁇ L water droplet so that the water droplet tumbles from the surface.
  • the surface shape of the undercoating film that is preferable for super-hydrophobicity can be achieved by mixing granular projections and columnar projections.
  • the surface of the hydrophobic surface preferably reflects this undercoat surface shape so that the surface of the hydrophobic film also has a mixture structure of granular projections and columnar projections. The structure easily holds air between a water droplet and the surface.
  • the columnar projections in the surface may be formed in single units, that is, integrated projections formed by irregular growth of minute particles in the thickness direction of the film.
  • the columnar projections may be formed by stacking microparticles on one another. There are no particular limitations with respect to the number and the configuration of the stacked microparticles.
  • the projections formed by stacking two or more microparticles in the thickness direction of the film protrude from the periphery, and more specifically, it is preferable that the columnar projections are contiguous bodies constituted by three or more microparticles in the thickness direction of the film, and whose periphery is surrounded by minute projections that in principle are the height of a single microparticle layer.
  • Dc and H When Dc is the diameter of the columnar projections and H is their height, Dc and H preferably satisfy: 2Dc ⁇ H and more preferably 3Dc ⁇ H.
  • values that are measured by SEM may be used for Dc and H.
  • Dc is preferably 10 nm to 200 nm, and the preferable range of H is normally 50 nm or more, although this depends on the value of Dc.
  • H is smaller than 50 nm, it is difficult to obtain super-hydrophobicity.
  • the hydrophobic film may include integral projections and projections formed by stacking microparticles.
  • the diameter Dp of the minute projections is preferably 5 nm to 200 nm.
  • a hydrophobic film forming solution should be applied while avoiding a mechanical contact with the undercoating film, so that the minute recesses and projections of the undercoating film are not destroyed.
  • the mechanical contact means a direct contact between the device for applying the solution and the film.
  • the minute projections are easily destroyed, especially immediately after their formation.
  • the stress to the film surface destroys the columnar projections, granular projections are hardly damaged.
  • the structure is superior in durability (abrasion resistance) to conventional super-hydrophobic articles.
  • the projections do not necessarily grow only perpendicular to the substrate surface, and there are also those that bend at an intermediate portion thereof in the lateral direction or those that grow obliquely from the start.
  • projections formed in this manner do not result in problems.
  • a coating solution is applied to a substrate surface and that solution is dried without sintering, and thus the substrate is not restricted.
  • the surface roughness of the film has an arithmetic mean roughness value (Ra) of preferably at least 10 nm, and the haze value of the film is preferably 1.0% or less and even more preferably 0.5% or less.
  • the diameter Dp of the minute projections is 200 nm or less and its average is 20 to 100 nm.
  • the diameter Dc should be 200 nm or less and its average is 20 to 100 nm so as to reduce the haze value.
  • the solution including a chlorosilyl-group containing compound as a solute is suitable.
  • the chlorosilyl-group containing compound should hold a chlorosilyl group in a nonaqueous solvent, and reacts with a hydrophilic group (—OH group) on a substrate surface to release hydrogen chloride and to be absorbed on the surface, when the solution is applied onto the substrate surface.
  • a hydrophilic group —OH group
  • the moisture in the air and the chlorosilyl group react to release hydrogen chloride and to generate a silanol group (—Si—OH).
  • chlorosilyl-group containing compound and the silanol-group containing compound would be absorbed alternately and layered naturally on a substrate surface while reacting and releasing hydrogen chloride.
  • the nonaqueous solvent for dissolving a chlorosilyl-group containing compound can be a solvent containing silicone oil as its main component.
  • the influence of the water included in the coating solution was investigated. After the moisture was absorbed in the solvent containing silicone oil as its main component, the solution including a chlorosilyl-group containing compound with the solvent was applied onto a substrate surface. As a result, the silica film obtained had granular projections, but was free from a columnar projection.
  • This solvent had a water content ratio of 0.035 mass %, and then it was found that the water content ratio of the solvent was preferably 0.03 mass % or smaller.
  • the moisture absorbed in the solvent in advance promotes the reaction between the moisture in the solution and the chlorosilyl group before the solution is applied. This inhibits the oligomers from precipitating on the substrate surface from the solution, and thus granular projections are formed, whereas columnar projections of layered granular projections are not formed.
  • the substrate surface is wet with the solution for at least one second, preferably at least one minute, so as to let the substrate surface absorb the chlorosilyl-group containing compounds naturally or to let the compounds stack on the surface.
  • the chlorosilyl-group containing compound When the substrate surface is wetted for a short time only, the chlorosilyl-group containing compound is not adequately adsorbed to the substrate surface, and thus a film having a structure of minute recesses and projections that confers super hydrophobicity cannot be obtained.
  • the same solution may be applied a second time after it has been applied to the substrate surface for a first time and preferably before the solution has dried completely.
  • the concentration of the chlorosilyl-group containing compound is preferably 0.01 to 10 mass % and more preferably 0.1 to 3 mass %, although this also differs depending on the application method.
  • the film becomes thick and turns into a white powder, and this is not preferable.
  • the concentration of the chlorosilyl-group containing compound is too high, the film becomes thick and turns into a white powder, and this is not preferable.
  • the concentration of the chlorosilyl-group containing compound is too low, the film does not have adequate thickness. As a result, a structure of minute recesses and projections that confers super hydrophobicity cannot be formed, and thus this is not preferable.
  • the chlorosilyl-group containing compound is dissolved in the solvent holding the chlorosilyl group.
  • the chlorosilyl-group containing compounds bind to the hydrophilic groups (—OH groups) of the substrate surface during application. Moreover, the chlorosilyl-group containing compounds bind to the substrate surface after undergoing hydrolysis and condensation polymerization due to the moisture in the air and the moisture adsorbed to the substrate surface. In this way, granular seeds 3 are formed scattered over the substrate surface (see FIG. 2A ).
  • the chlorosilyl-group containing compounds proceed from hydrolysis with the moisture in the air to a condensation reaction, generating oligomers of silicon oxide. Once these oligomers have grown to a size where they do not dissolve in the solvent, they start to precipitate out of the solvent, and the oligomers 4 that have precipitated accumulate and grow as projections ( FIG. 2B ).
  • silanol Si—OH group
  • the oligomers 6 also bind the Si—Cl or Si—OH groups on the surface with recesses and projections before precipitating, and projections are grown from the surface as well ( FIG. 2C ).
  • the difference between the projections grown from the substrate surface and formed in a single unit and the projections that are formed as grains pile on one another is due to the ratio of the amount of precipitated oligomers that are accumulated and the amount of dissolved raw material that precipitates directly onto the substrate surface, and on the density of the seeds that are formed immediately after application.
  • the application method it is necessary that the application solution wets the substrate surface evenly.
  • Specific examples of the application method include a flow coating method, a dip coating method, a curtain coating method, a spin coating method, a spray coating method, a bar coating method, and an immersion and adsorption method. Of these methods, a flow coating method and a spray coating method are preferable because they allow efficient application.
  • the chlorosilyl-group containing compound for the present invention is a compound that includes at least one chlorosilyl group (—SiCl n X 3 ⁇ n , where n is 1, 2, or 3, and X is hydrogen or an alkyl group, alkoxyl group, or acyloxy group with a carbon number of 1 to 10) within the molecule.
  • a compound that includes at least two chlorine atoms is preferable, and a chlorosilane in which at least two of the hydrogen atoms of silane Si n H 2n+2 (wherein n is an integer of 1 to 5) are substituted with chlorine atoms and the other hydrogen atoms are substituted with an alkyl group, an alkoxyl group, or an acyloxy group where necessary, and partial hydrolyzates and condensates thereof, are preferable.
  • tetrachlorosilane SiCl 4
  • trichlorosilane SiHCl 3
  • trichloromonomethylsilane SiCH 3 Cl 3
  • dichlorosilane SiH 2 Cl 2
  • Cl—(SiCl 2 O) n —SiCl 3 wherein n is an integer of 1 to 10. Any of these may be used alone or a plurality thereof may be used in combination, but the most preferable chlorosilyl-group containing compound is tetrachlorosilane.
  • the solvent having silicone oil as its main component is preferably acyclic and/or cyclic dimethyl silicone oil.
  • examples thereof include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. These may be used alone or a plurality thereof may be used in combination.
  • the environment for the application process is preferably a temperature of 10° C. to 40° C. and a relative humidity (RH) of 15% to 60%, and more preferably is a temperature of 15° C. to 25° C. and a relative humidity (RH) of 20% to 40%. Columnar projections are not formed when the temperature and the humidity are too low.
  • Examples of a hydrophobic group that exhibits hydrophobicity include a fluoroalkyl group or an alkyl group.
  • the hydrophobic material is preferably a silane compound that includes a fluoroalkyl group or an alkyl group and that includes a hydrolysable group that matches well with the chlorosilyl group formed in advance on the substrate surface.
  • Examples of the hydrolysable group include an alkoxyl group, an acyloxy group, and a chlorine group.
  • silane compounds including the hydrolysable group it is possible to use hydrolyzates that are partially hydrolyzed and polymers that have been polymerized by condensation. Of these, a silane compound including a fluoroalkyl group, which has excellent hydrophobicity, is especially preferable.
  • fluoroalkyl group-containing silane compounds examples include silane compounds that contain a fluoroalkyl group and that also contain an alkoxyl group, an acyloxy group, or a chlorine group. Possible examples include CF 3 (CF 2 ) 7 (CH 2 ) 2 Si(OCH 3 ) 3 , CF 3 (CF 2 ) 5 (CH 2 ) 2 Si(OCH 3 ) 3 , CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 , and CF 3 (CF 2 ) 5 (CH 2 ) 2 SiCl 3 .
  • CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 is most preferable because of its particularly high reactivity and hydrophobicity.
  • a chlorosilyl-group containing compound that is formed on the substrate first is applied by being dissolved in a solvent having silicone oil as its main component, and thus the hydrophobic agent that is applied afterwards is preferably a nonaqueous solvent, which belongs to the same group.
  • nonaqueous solvent examples include paraffin-based hydrocarbons, flon-based solvents, and solvents containing silicone oil as their main component.
  • solvents containing silicone oil as their main component are preferable because such solvents are the same as the solvent in which the chlorosilyl-group containing compound that is formed on the substrate surface first is dissolved.
  • hydrophobic solution it is necessary that the surface structure of the film with recesses and projections formed first is not destroyed. More specifically, it is preferable that the hydrophobic solution is adsorbed in the same manner as the chlorosilyl-group containing compound that is formed first. To adsorb the hydrophobic solution, it is necessary for the substrate surface to be wetted with the hydrophobic solution for at least 0.1 seconds after the hydrophobic solution is applied.
  • the hydrophobic solution should be applied in a thickness such that the hydrophobic film reflects the minute recesses and projections of the undercoating film. It is sufficient that a single layer of the hydrophobic material is bonded, unlike the chlorosilyl-group containing compound of the film with recesses and projections that is formed first, and thus the period during which the substrate is wetted with the hydrophobic solution can be shorter than the period during which the chlorosilyl-group containing compound is allowed to adhere naturally to and form layers on the substrate surface. However, when this period is less than 0.1 seconds, the hydrophobic material is not adequately adsorbed, and thus suitable hydrophobicity cannot be exhibited.
  • the solution for forming the functional film may be applied avoiding mechanical contact with the undercoating film, so that the minute recesses and projections of the undercoating film formed first are not destroyed.
  • the method can be a flow coating method, a dip coating method, a curtain coating method, a spin coating method, a spray coating method, a bar coating method, and an immersion and adsorption method.
  • a flow coating method and a spray coating method are preferable because they allow efficient application.
  • Examples of materials for the substrate include glass and resin, and transparent materials are preferable. It is preferable that a material having hydrophilic groups in its surface is used.
  • Specific examples of the substrate include a glass substrate, a resin substrate, and a resin film. Mirrors for vehicles also can be used for the substrate.
  • the surface may be made hydrophilic by processing it in advance in a plasma or corona atmosphere including oxygen.
  • the solution may be applied after the substrate surface has been provided with hydrophilicity by irradiating ultraviolet radiation of a wavelength around 200 to 300 nm in an oxygen-containing atmosphere.
  • the super-hydrophobic film can be formed by applying a coating solution to a substrate surface and drying it at a room temperature, and thus the film can be formed on any kind of substrates. It is possible to adopt the present invention for a transparent glass sheet attached to a vehicle body.
  • the super-hydrophobic film may be formed on a resin film by the present invention, and then the film may be attached to the transparent glass sheet.
  • silicon does not strictly refer to objects in the state of SiO 2 , and is used simply to mean silicon oxides.
  • tetrachlorosilane SiCl 4 ; made by Shin-Etsu Silicones
  • KF-995 decamethylcyclopentasiloxane
  • the coating solution for forming an undercoating film was applied onto the surface of a washed windshield glass for automobiles at a relative humidity of 30% and at room temperature using flow coating, and for a period of one minute the glass surface was allowed to sit, being wetted by this solution.
  • the same solution was then applied a second time using flow coating, and for a period of one minute the glass surface wetted by this solution was allowed to sit.
  • the hydrophobicity providing agent was applied onto the glass surface using flow coating when the glass surface was still wet with the coating solution for forming an undercoating film, and for a period of one minute the glass surface wetted by the agent was allowed to sit.
  • the agent was completely washed away with ethanol and drying was allowed to occur naturally, yielding a windshield glass provided with hydrophobicity.
  • the surface configuration of the windshield glass provided with hydrophobicity that was obtained in this manner was observed using a scanning electron microscope (SEM) “S-4700 model” manufactured by Hitachi Seisakusho Inc., under the following conditions: acceleration voltage of 5 kV, emission current of 10 ⁇ A, slope angle of 10°, zoom factor of 100,000 times magnification. The result is shown in FIG. 3 . It is clear from the result that minute granular projections and columnar projections were formed in the surface of the hydrophobic film.
  • SEM scanning electron microscope
  • FIG. 3 indicates that the columnar projections are constituted by microparticles grown irregularly in the film thickness direction of the film, and more specifically has a shape in which they grow to two or three times or more the average height of the minute projections made of microparticles.
  • the columnar projections were formed on less than half the area of the overall region, and the remainder was covered by minute projections.
  • the height H of some of the columnar projections from the substrate surface was found to be at least three times their average diameter Dc. H, Dc, and the diameter Dp of the minute projections were within the above-mentioned preferable range.
  • the average values of Dp and Dc were both within the range of 20 nm to 100 nm.
  • the arithmetic mean roughness value Ra was measured using an atomic force microscope (AFM), “SPI3700” manufactured by Seiko Instruments Inc., in cyclic contact mode. The larger the value of the Ra is, the greater the unevenness of the film surface is.
  • the hydrophobicity of the windshield glass provided with hydrophobicity was evaluated through the contact angle and the tumbling angle of water. Using a contact angle meter “CA-DT” made by Kyowa Interface Science Co., Ltd., a 4 ⁇ L water droplet was dropped onto the surface of the glass substrate, and the passive contact angle was measured. The smaller the value of the contact angle is, the greater the hydrophilicity is.
  • the transparency of the windshield glass provided with hydrophobicity was evaluated using the haze value.
  • the haze value was measured using a direct reading haze computer “HGM-2DM” manufactured by Suga Test Instruments Co., Ltd. The smaller the haze value is, the higher the transparency of the film is.
  • the abrasion resistance of the film of the windshield glass provided with hydrophobicity were evaluated.
  • a dry towel was attached to a reciprocating abrasion tester (manufactured by Shinto Scientific Co., Ltd.), and with a load of 125 g/cm 2 , the glasses provided with hydrophobicity were slid back and forth 100 times and then the contact angle of water on the glass provided with hydrophobicity was measured.
  • a solution for forming an undercoating film with minute recesses and projections that was prepared in the same manner as in Example 1 was applied onto the surface of a washed windshield glass at a relative humidity of 30% and at room temperature using flow coating, and for a period of one second the glass surface was allowed to sit, being wetted by this solution. Then, the hydrophobicity providing agent was applied onto the glass surface using flow coating when the glass surface was still wet with the coating solution, and for a period of one minute the glass surface wetted by the agent was allowed to sit. The agent was completely washed away with ethanol and drying was allowed to occur naturally, yielding a windshield glass provided with hydrophobicity.
  • a solution for forming an undercoating film with minute recesses and projections that was prepared in the same manner as in Example 1 was applied onto the surface of a washed windshield glass at a relative humidity of 30% and at room temperature using flow coating, and for a period of 10 seconds the glass surface was allowed to sit, being wetted by this solution. Then, the hydrophobicity providing agent was applied onto the glass surface using flow coating when the glass surface was still wet with the coating solution, and for a period of one minute the glass surface wetted by the agent was allowed to sit. The agent was completely washed away with ethanol and drying was allowed to occur naturally, yielding a windshield glass provided with hydrophobicity.
  • tetrachlorosilane SiCl 4 ; made by Shin-Etsu Silicones
  • KF-995 decamethylcyclopentasiloxane
  • the coating solution for forming an undercoating film was applied onto the surface of a washed windshield glass for automobiles at a relative humidity of 30% and at room temperature using flow coating, and for a period of one minute the glass surface was allowed to sit, being wetted by this solution. Then, the hydrophobicity providing agent was applied onto the glass surface using flow coating when the glass surface was still wet with the coating solution for forming an undercoating film, and for a period of one minute the glass surface wetted by this solution was allowed to sit. The agent was completely washed away with ethanol and drying was allowed to occur naturally, yielding a windshield glass provided with hydrophobicity.
  • tetrachlorosilane SiCl 4 ; made by Shin-Etsu Silicones
  • KF-995 decamethylcyclopentasiloxane
  • the coating solution for forming an undercoating film was applied onto the surface of a washed windshield glass for automobiles at a relative humidity of 30% and at room temperature using flow coating, and for a period of five minutes the glass surface was allowed to sit, being wetted by this solution.
  • the same solution was then applied a second time using flow coating, and for a period of five minutes the glass surface was allowed to sit, wetted by this solution.
  • the hydrophobicity providing agent which was prepared in the same manner as in Example 1, was applied onto the glass surface using flow coating when the glass surface was still wet with the coating solution for forming an undercoating film, and for a period of one minute the glass surface wetted by this solution was allowed to sit.
  • the agent was completely washed away with ethanol and drying was allowed to occur naturally, yielding a windshield glass provided with hydrophobicity.
  • Example 5 The surface configuration of the glass sheet provided with hydrophobicity that was obtained in this manner was observed using a scanning electron microscope under the same conditions as in Example 1 (see FIG. 5 ).
  • the columnar projections are constituted by stacked microparticles.
  • the columnar projections include projections made of three or more microparticles that are stacked locally and protrude from the surrounding particles as a protrusion of two or more stacked microparticles.
  • the columnar projections were formed on less than half the area of the overall region, and the remainder was covered by minute projections.
  • the height H of some of the columnar projections from the substrate surface was found to be at least three times their average diameter Dc.
  • H, Dc, and the diameter Dp of the minute projections were within the above-mentioned preferable range.
  • the average value of Dp and Dc were both within the range of 20 nm to 100 nm.
  • a windshield glass provided with hydrophobicity was obtained in the same manner as in Example 1 except that the humidity during the application of the coating solution for forming an undercoating film that was prepared in the same manner as in Example 1 was changed to 15%.
  • a windshield glass provided with hydrophobicity was obtained in the same manner as in Example 1 except that the coating solution for forming an undercoating film that was prepared in the same manner as in Example 1 was applied on a windshield glass that was attached to a automobile body.
  • Ra in all the films is 10 nm or more and the films had large surface roughness.
  • Table 1 shows the following properties in Examples 1 to 7: Surface roughness, Initial water repellency (contact/tumbling angle), Contact angle after abrasion test, Haze value, and Visibility in a light rain. TABLE 1 Initial water Contact Surface repellency angle after Haze Visibility Ex. roughness (contact angle/ abrasion value in a light No.
  • the windshield glass provided with hydrophobicity obtained in Examples 1 to 7 satisfied the following relationships: CA ⁇ 150° and TA ⁇ 15°; or 150°>CA ⁇ 145° and TA ⁇ 5°, where CA is a contact angle and TA is a tumbling angle.
  • the contact angles after the abrasion test were at least 1000, exhibiting normal hydrophobicity, which indicated that excellent abrasion resistance was provided, although it did not reach super-hydrophobicity.
  • the haze values were no greater than 1.0%, exhibiting high transparency, and the transparent color tones and reflect color tones were neutral, indicating that there were no problems in appearance. Further, in a light rain, water droplets hardly remained on the windshields provided with hydrophobicity that were attached to an actual automobile, and excellent visibility was provided.
  • a windshield glass provided with hydrophobicity was obtained in the same manner as in Example 4 except that the period was changed from one minute to one second, for which the glass surface was allowed to sit in a wet state with a coating solution for forming an undercoating film that was prepared in the same manner as in Example 4.
  • the windshield glass provided with hydrophobicity that was obtained in this manner was evaluated in the same manned as in Examples 1 to 7
  • the initial contact angle was 142° and the initial tumbling angle was 17.8°, which indicates that it is inferior in water repellency.
  • water droplets remained on the surface of the windshield that was attached to an actual automobile body, exhibiting poor visibility.
  • the coating solution for forming the undercoating film was applied onto the surface of a washed windshield glass for automobiles at a relative humidity of 30% and at room temperature using flow coating, and for a period of five minutes the glass surface was allowed to sit, being wetted by this solution. Then, the hydrophobicity providing agent that was prepared in the same manner as in Example 1 was applied onto the glass surface using flow coating when the glass surface was still wet with the coating solution for forming an undercoating film, and for a period of one minute the glass surface wetted by this solution was allowed to sit. The agent was completely washed away with ethanol and drying was allowed to occur naturally, yielding a windshield glass provided with hydrophobicity.
  • the windshield glass provided with hydrophobicity that was obtained in this manner was evaluated in the same manned as in Examples 1 to 7
  • the initial contact angle was 123° and the initial tumbling angle was 16.6°, which indicates that it is inferior in water repellency.
  • White powder was locally observed on the film, and its haze value was 3.8%, exhibiting poor transparency. In a light rain, water droplets remained on the surface of the windshield that was attached to an actual automobile body, exhibiting poor visibility.
  • a windshield glass provided with hydrophobicity was obtained in the same manner as in Example 1 except that decamethylcyclopentasiloxane was substituted with isoparaffin based solvent (Isozol 300: made by Nippon Petrochemicals Co., Ltd.).
  • the windshield glass provided with hydrophobicity that was obtained in this manner was evaluated in the same manned as in Examples 1 to 7
  • the initial contact angle was 91° and the initial tumbling angle was 12.8°, which indicates that it was inferior in water repellency.
  • water droplets remained on the surface of the windshield that was attached to an actual automobile body, exhibiting poor visibility.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Glass (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
US10/494,867 2001-11-08 2002-11-08 Ultra-water-repellent substrate Abandoned US20050008876A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2001343639 2001-11-08
JP2001-343639 2001-11-08
JP2001384104 2001-12-18
JP2001-384104 2001-12-18
PCT/JP2002/011638 WO2003039856A1 (fr) 2001-11-08 2002-11-08 Substrat ultra hydroresistant

Publications (1)

Publication Number Publication Date
US20050008876A1 true US20050008876A1 (en) 2005-01-13

Family

ID=26624425

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/479,142 Expired - Fee Related US7022416B2 (en) 2001-11-08 2002-11-08 Article coated with coating film, and functional article coated with coating film using the same
US10/494,867 Abandoned US20050008876A1 (en) 2001-11-08 2002-11-08 Ultra-water-repellent substrate

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US10/479,142 Expired - Fee Related US7022416B2 (en) 2001-11-08 2002-11-08 Article coated with coating film, and functional article coated with coating film using the same

Country Status (6)

Country Link
US (2) US7022416B2 (fr)
EP (2) EP1449641A4 (fr)
JP (1) JP4198598B2 (fr)
KR (1) KR20040052516A (fr)
CN (1) CN1538909A (fr)
WO (2) WO2003039856A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060292369A1 (en) * 2005-03-10 2006-12-28 Rutledge Gregory C Superhydrophobic fibers and methods of preparation and use thereof
US20070048249A1 (en) * 2005-08-24 2007-03-01 Purdue Research Foundation Hydrophilized bactericidal polymers
US20070166464A1 (en) * 2003-09-02 2007-07-19 Kazim Acatay Process for preparing superhydrophobic surface compositions, surfaces obtained by said process and use of them
US20080304008A1 (en) * 2005-12-15 2008-12-11 Essilor International (Compagnie Generale D'optique) Article Coated With an Ultra High Hydrophobic Film and Process For Obtaining Same
US20100021692A1 (en) * 2006-09-21 2010-01-28 Edward Bormashenko Superhydrophobic nanotextured polymer and metal surfaces
US20100028604A1 (en) * 2008-08-01 2010-02-04 The Ohio State University Hierarchical structures for superhydrophobic surfaces and methods of making
US20110104439A1 (en) * 2008-07-04 2011-05-05 Hyeon Choi Transparent water-repellent glass and method of manufacture thereof
US20150329755A1 (en) * 2012-12-27 2015-11-19 Jgc Catalysts And Chemicals Ltd. Water-Repellant Transparent Coating-Substrate Assembly and Process for Producing the Same
US20180158569A1 (en) * 2016-12-06 2018-06-07 Yazaki Corporation Electric wire with terminal, method for manufacturing electric wire with terminal and wire harness
US20230037586A1 (en) * 2021-08-02 2023-02-09 University Of Iowa Research Foundation Method for maskless patterning of metal alloys

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1538909A (zh) * 2001-11-08 2004-10-20 日本板硝子株式会社 皮膜覆盖物品、以及使用它的功能性皮膜覆盖物品
GB0206930D0 (en) 2002-03-23 2002-05-08 Univ Durham Method and apparatus for the formation of hydrophobic surfaces
CN1860083A (zh) * 2003-09-25 2006-11-08 日本板硝子株式会社 功能性玻璃物品及其制造方法
JP2005317796A (ja) * 2004-04-28 2005-11-10 Toshiba Corp ポンプ、冷却装置および電子機器
DE602005003234T2 (de) 2004-07-12 2008-08-28 Cardinal Cg Co., Eden Prairie Wartungsarme beschichtungen
DE102004053707B8 (de) * 2004-11-03 2008-08-28 Schott Ag Verfahren zur Herstellung eines Glaskeramik-Artikels mit Diffusionsbarriere und Verwendung eines verfahrensgemäß hergestellten Glaskeramik-Artikels
WO2006089964A1 (fr) * 2005-02-28 2006-08-31 Glaverbel Substrat pour revêtement hydrophobe
US20060216476A1 (en) * 2005-03-28 2006-09-28 General Electric Company Articles having a surface with low wettability and method of making
CN100439091C (zh) * 2005-06-03 2008-12-03 中国科学院化学研究所 一种仿生集水复合薄膜的制备方法
US8067065B2 (en) * 2005-12-08 2011-11-29 Toyota Motor Engineering & Manufacturing North America, Inc. Fibrillar, nanotextured coating and method for its manufacture
WO2007121211A2 (fr) * 2006-04-11 2007-10-25 Cardinal Cg Company Revêtements photocatalytiques dotés de propriétés améliorées permettant un entretien minime
US20080011599A1 (en) 2006-07-12 2008-01-17 Brabender Dennis M Sputtering apparatus including novel target mounting and/or control
EP2116518A1 (fr) 2006-12-15 2009-11-11 Asahi Glass Company, Limited Articles ayant des surfaces hydrophobes
US20100034335A1 (en) * 2006-12-19 2010-02-11 General Electric Company Articles having enhanced wettability
WO2008131063A1 (fr) * 2007-04-19 2008-10-30 3M Innovative Properties Company Procédés d'utilisation d'un matériau de support solide destiné à lier des biomolécules
CN101663581A (zh) * 2007-04-19 2010-03-03 3M创新有限公司 水分散性二氧化硅纳米颗粒在连接生物分子方面的用途
WO2009036284A1 (fr) 2007-09-14 2009-03-19 Cardinal Cg Company Revêtements à faible entretien et procédés de production de revêtements à faible entretien
CN101469250B (zh) 2007-12-26 2012-09-19 3M创新有限公司 可去除的防雾涂层、制品、涂料组合物和方法
FR2928642B1 (fr) * 2008-03-11 2012-07-27 Saint Gobain Substrat verrier a hydrophobie persistante a haute temperature
US8286561B2 (en) 2008-06-27 2012-10-16 Ssw Holding Company, Inc. Spill containing refrigerator shelf assembly
US11786036B2 (en) 2008-06-27 2023-10-17 Ssw Advanced Technologies, Llc Spill containing refrigerator shelf assembly
WO2010042191A1 (fr) 2008-10-07 2010-04-15 Ross Technology Corporation Revêtements super hydrophobes, oléophobes et antigivre à haute durabilité, et procédés et compositions pour leur préparation
US8701927B2 (en) * 2009-02-11 2014-04-22 Massachusetts Institute Of Technology Nanoparticle thin-film coatings for enhancement of boiling heat transfer
CN101941001B (zh) 2009-07-03 2014-04-02 3M创新有限公司 亲水涂层、制品、涂料组合物和方法
US7973997B2 (en) * 2009-08-31 2011-07-05 Korea University Research And Business Foundation Transparent structures
WO2011056742A1 (fr) 2009-11-04 2011-05-12 Ssw Holding Company, Inc. Surfaces d'appareils de cuisson ayant une configuration permettant la retenue des débordements et procédés de fabrication de ces surfaces
BR112012023312A2 (pt) 2010-03-15 2019-09-24 Ross Tech Corporation desentupidor e métodos de produção de superfícies hidrofóbicas
NL2006506A (en) * 2010-04-28 2011-10-31 Asml Netherlands Bv A component of an immersion system, an immersion lithographic apparatus and a device manufacturing method.
CN102241899B (zh) 2010-05-11 2014-05-14 3M创新有限公司 涂料组合物，改性基体表面的方法和制品
DK2616230T3 (en) 2010-09-15 2018-03-26 Jeld Wen Inc Method and System for Manufacturing a Moisture Resistant Thin Layer Fiber Composite Material
EP2463081A1 (fr) 2010-12-09 2012-06-13 3M Innovative Properties Co. Système comprenant un dispositif de prototypage rapide et une cartouche de matériau, cartouche et procédé d'utilisation du système
AU2012220798B2 (en) 2011-02-21 2016-04-28 Ross Technology Corporation Superhydrophobic and oleophobic coatings with low VOC binder systems
DE102011085428A1 (de) 2011-10-28 2013-05-02 Schott Ag Einlegeboden
WO2013090939A1 (fr) 2011-12-15 2013-06-20 Ross Technology Corporation Composition et revêtement pour une performance superhydrophobe
CA2878189C (fr) 2012-06-25 2021-07-13 Ross Technology Corporation Revetements elastomeres ayant des proprietes hydrophobes et/ou oleophobes
JP6214281B2 (ja) * 2013-08-30 2017-10-18 クラリオン株式会社 車載用カメラ
CN105683302A (zh) 2013-10-04 2016-06-15 3M创新有限公司 可涂覆型组合物、防静电组合物、防静电制品及它们的制备方法
DE102014220798A1 (de) 2014-10-14 2016-04-14 Scheuten S.À.R.L. Hydrophil beschichtetes Isolierglas für Gewächshäuser
WO2016080432A1 (fr) * 2014-11-20 2016-05-26 旭硝子株式会社 Plaque transparente, pavé tactile et écran tactile
CN105486610B (zh) * 2015-11-22 2018-11-27 沈阳黎明航空发动机(集团)有限责任公司 一种憎水涂层的制备及憎水性能评价方法
EP3541762B1 (fr) 2016-11-17 2022-03-02 Cardinal CG Company Technologie de revêtement à dissipation statique
JP7135851B2 (ja) 2018-04-11 2022-09-13 信越化学工業株式会社 撥水性被膜形成用組成物及び撥水性被膜
EP3553121B1 (fr) 2018-04-11 2021-06-09 Shin-Etsu Chemical Co., Ltd. Composition de formation de film hydrofuge et film hydrofuge
WO2020196870A1 (fr) * 2019-03-28 2020-10-01 日鉄ステンレス株式会社 Feuille d'acier inoxydable revêtue transparente

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6800354B2 (en) * 2000-12-21 2004-10-05 Ferro Gmbh Substrates with a self-cleaning surface, a process for their production and their use
US7022416B2 (en) * 2001-11-08 2006-04-04 Nippon Sheet Glass Company, Limited Article coated with coating film, and functional article coated with coating film using the same

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2767633B2 (ja) * 1989-11-21 1998-06-18 株式会社コーセー ゲル組成物及びこれを含有する化粧料
CA2054094C (fr) * 1990-10-25 1999-12-21 Kazufumi Ogawa Pellicule de lamination monomoleculaire adsorbee chimiquement
JP3245972B2 (ja) 1992-07-08 2002-01-15 松下電器産業株式会社 超撥水性フィルムの製造方法
JPH1045429A (ja) * 1996-07-29 1998-02-17 Nippon Sheet Glass Co Ltd 撥水性物品およびその製造方法
US6156409A (en) * 1996-12-09 2000-12-05 Nippon Sheet Glass Co., Ltd. Non-fogging article and process for the production thereof
JP3334611B2 (ja) * 1997-06-24 2002-10-15 日本板硝子株式会社 撥水性物品の製造方法、撥水性物品および撥水性被膜形成用溶液
JP2000144116A (ja) * 1998-11-10 2000-05-26 Central Glass Co Ltd 超撥水性被膜
JPH11286784A (ja) * 1999-02-18 1999-10-19 Kansai Shingijutsu Kenkyusho:Kk ガラスの表面改質方法
JP4247354B2 (ja) 1999-07-08 2009-04-02 財団法人大阪産業振興機構 表面微細凹凸組織の低温形成法および当該組織を有する基体
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6800354B2 (en) * 2000-12-21 2004-10-05 Ferro Gmbh Substrates with a self-cleaning surface, a process for their production and their use
US7022416B2 (en) * 2001-11-08 2006-04-04 Nippon Sheet Glass Company, Limited Article coated with coating film, and functional article coated with coating film using the same

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070166464A1 (en) * 2003-09-02 2007-07-19 Kazim Acatay Process for preparing superhydrophobic surface compositions, surfaces obtained by said process and use of them
WO2006099107A3 (fr) * 2005-03-10 2007-09-07 Massachusetts Inst Technology Fibres superhydrophobes, et leurs procedes de preparation et d'utilisation
US20060292369A1 (en) * 2005-03-10 2006-12-28 Rutledge Gregory C Superhydrophobic fibers and methods of preparation and use thereof
US8574713B2 (en) 2005-03-10 2013-11-05 Massachusetts Institute Of Technology Superhydrophobic fibers and methods of preparation and use thereof
US20070048249A1 (en) * 2005-08-24 2007-03-01 Purdue Research Foundation Hydrophilized bactericidal polymers
US20130095290A1 (en) * 2005-12-15 2013-04-18 Essilor International (Compagnie Generale D'optique) Article Coated with an Ultra High Hydrophobic Film and Process for Obtaining Same
US20080304008A1 (en) * 2005-12-15 2008-12-11 Essilor International (Compagnie Generale D'optique) Article Coated With an Ultra High Hydrophobic Film and Process For Obtaining Same
US20100021692A1 (en) * 2006-09-21 2010-01-28 Edward Bormashenko Superhydrophobic nanotextured polymer and metal surfaces
US9587304B2 (en) 2006-09-21 2017-03-07 Ariel-University Research And Development Company Ltd. Superhydrophobic nanotextured polymer and metal surfaces
US20110104439A1 (en) * 2008-07-04 2011-05-05 Hyeon Choi Transparent water-repellent glass and method of manufacture thereof
US20110177288A1 (en) * 2008-08-01 2011-07-21 Bharat Bhushan Hierarchical structures for superhydrophobic surfaces and methods of making
US8137751B2 (en) 2008-08-01 2012-03-20 The Ohio State University Hierarchical structures for superhydrophobic surfaces and methods of making
US20100028604A1 (en) * 2008-08-01 2010-02-04 The Ohio State University Hierarchical structures for superhydrophobic surfaces and methods of making
US20150329755A1 (en) * 2012-12-27 2015-11-19 Jgc Catalysts And Chemicals Ltd. Water-Repellant Transparent Coating-Substrate Assembly and Process for Producing the Same
US9856407B2 (en) * 2012-12-27 2018-01-02 Jgc Catalysts And Chemicals Ltd. Water-repellant transparent coating-substrate assembly and process for producing the same
US20180158569A1 (en) * 2016-12-06 2018-06-07 Yazaki Corporation Electric wire with terminal, method for manufacturing electric wire with terminal and wire harness
US20230037586A1 (en) * 2021-08-02 2023-02-09 University Of Iowa Research Foundation Method for maskless patterning of metal alloys

Also Published As

Publication number Publication date
EP1449642A4 (fr) 2007-06-13
WO2003039856A1 (fr) 2003-05-15
US7022416B2 (en) 2006-04-04
US20040170844A1 (en) 2004-09-02
EP1449641A1 (fr) 2004-08-25
KR20040052516A (ko) 2004-06-23
EP1449642A1 (fr) 2004-08-25
WO2003039855A1 (fr) 2003-05-15
JP4198598B2 (ja) 2008-12-17
CN1538909A (zh) 2004-10-20
JPWO2003039856A1 (ja) 2005-02-24
EP1449641A4 (fr) 2007-06-13

Similar Documents

Publication Publication Date Title
US20050008876A1 (en) Ultra-water-repellent substrate
US6033738A (en) Method for producing water-repellent articles, water-repellent articles obtained thereby, and solution for forming water-repellent film
KR100482261B1 (ko) 요철부를포함하는기판,그사용방법과제조방법및상기기판에코팅을형성하는방법
CA2423657C (fr) Revetements hydrophobes a haute durabilite et procedes associes
JP5716679B2 (ja) 撥水性基体およびその製造方法
JP3588364B2 (ja) 表面処理された基材および基材の表面処理方法
US20080248263A1 (en) Method of creating super-hydrophobic and-or super-hydrophilic surfaces on substrates, and articles created thereby
JP4279064B2 (ja) 多孔性シリカ膜、それを有する積層体
JPH0597478A (ja) 撥水性ガラス物品およびその製造方法
JP4256662B2 (ja) 皮膜被覆物品、およびその製造方法
JP2545642B2 (ja) ガラス
US20150079348A1 (en) Antireflection film and method for producing the same
EP0967297A1 (fr) Procede de production d'articles recouvertes d'enrobages a base de silice
JP2004136630A (ja) 機能性皮膜被覆物品、およびその製造方法
JP4279063B2 (ja) 多孔性シリカ膜、それを有する積層体
JP3427755B2 (ja) シリカ系膜被覆物品を製造する方法
JPH11171594A (ja) 撥水性ガラス物品およびその製造方法
JPH0812375A (ja) 撥水性物品及びその製造方法
JP2001205187A (ja) シリカ系膜被覆物品の製造方法、およびシリカ系膜被覆物品
JPH09202651A (ja) 親水性被膜及びその形成法
JP3982426B2 (ja) シリカ系膜被覆物品
JP3961349B2 (ja) 高耐久性滑水被膜及びその製造方法
JP2001172417A (ja) 撥水膜被覆物品の製造方法、およびそれに用いる撥水膜被覆用液組成物
JP3598529B2 (ja) 撥水性物品の製造方法
JP4152769B2 (ja) 高耐久な滑水性被膜の製造方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: NIPPON SHEET GLASS COMPANY, LIMITED, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:TERANISHI, TOYOYUKI;REEL/FRAME:015775/0828

Effective date: 20040420

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION