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WO2024176509A1 - Film hydrofuge et procédé de fabrication dudit film - Google Patents

Film hydrofuge et procédé de fabrication dudit film Download PDF

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Publication number
WO2024176509A1
WO2024176509A1 PCT/JP2023/036554 JP2023036554W WO2024176509A1 WO 2024176509 A1 WO2024176509 A1 WO 2024176509A1 JP 2023036554 W JP2023036554 W JP 2023036554W WO 2024176509 A1 WO2024176509 A1 WO 2024176509A1
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WIPO (PCT)
Prior art keywords
water
frame portion
repellent film
film
recesses
Prior art date
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Ceased
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PCT/JP2023/036554
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English (en)
Japanese (ja)
Inventor
世維 片木
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Publication date
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Publication of WO2024176509A1 publication Critical patent/WO2024176509A1/fr
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    • 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
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof

Definitions

  • the present invention relates to a water-repellent film and a method for producing the water-repellent film.
  • Water-repellent films have traditionally been used for a variety of purposes, including as anti-reflective coatings, scaffolds for cell culture, battery materials, films to prevent oil adhesion, and inkjet liquid ejection heads.
  • Patent Document 1 discloses a resin composition containing a fluorine-containing polystyrene derivative containing 1% by mass or more of a specific repeating unit and a thermoplastic resin, the polystyrene derivative being contained in an amount of 0.01% by mass or more and 99.0% by mass or less relative to the total mass of the polystyrene derivative and the thermoplastic resin, and the resin composition is applied to a substrate to form a coating film, the surface of which has a water contact angle of 100° or more or a hexadecane contact angle of 50° or more, or a water contact angle of 100° or more and a hexadecane contact angle of 50° or more.
  • Patent Document 2 discloses a water-repellent surface structure having a concave-convex structure formed directly on the surface of a substrate, characterized in that the plateau structure surface forming the surface of the concave-convex structure has a grating-like periodic structure in which the apexes of the convex portions are non-flat and the height changes continuously.
  • Patent Document 3 discloses a highly adhesive, super-water-repellent substrate having a super-water-repellent pillar structure formed on a substrate from a hydrophobic polymer, the pillar structure being fixed to the substrate with an adhesive, and the pillar structure having a hydrophilic metal partially therein.
  • Patent Document 4 discloses a method for producing a water-repellent film, which includes a polymer solution coating film forming step of coating a first substrate with a polymer solution in which a hydrophobic polymer is dissolved in an organic solvent to form a polymer solution coating film; a water droplet forming step of supplying a water droplet forming atmosphere to the surface of the polymer solution coating film to form water droplets on the surface of the polymer solution coating film; a recess forming step of evaporating the organic solvent and the water droplets to form multiple recesses in the polymer coating film using the polymer coating film surface as a reference plane; a first protrusion structure forming step of attaching a second substrate to the multiple recesses via an adhesive, peeling off the second substrate to peel off at least the surface portions of the multiple recesses in the thickness direction, and forming multiple first protrusion structures on the second substrate; and a second substrate etching step of etching the second substrate using the multiple first protrusion structures as
  • Patent Document 1 describes the formation of a water-repellent coating film by applying a resin composition containing a fluorine-containing polystyrene derivative to a substrate, but the water repellency of the coating film is not sufficiently high, and there is room for improvement.
  • Patent Document 2 water repellency is improved by increasing the surface area ratio while reducing the height of the convex portions of the uneven structure.
  • Patent Document 2 laser processing is used to form the uneven structure, but this has the problem of high processing costs.
  • the highly adhesive, superhydrophobic substrate of Patent Document 3 has a superhydrophobic pillar structure made of a hydrophobic polymer (resin), which has the problem of being weak and vulnerable to external forces such as rubbing.
  • the method for producing a micro-relief structure in Patent Document 4 makes it possible to produce a water-repellent film, but it requires complicated processes such as adhesion, peeling, and etching, and has a large environmental impact, making it unsuitable for practical use.
  • the micro-relief structure described in Patent Document 4 is made of a polymer (resin), and has the problem of being weak in strength.
  • the present invention has been made to solve the above problems, and the object of the present invention is to provide a water-repellent film that can be easily manufactured at low cost and has sufficiently high strength, and a method for manufacturing said water-repellent film.
  • the water-repellent film of the present invention is composed of a film-like frame part having a plurality of droplet-shaped recesses formed on one of its main surfaces, the frame part being a porous ceramic sintered body, and the frame part is composed of a concave-convex structure in which the average maximum depth of the recesses in the thickness direction of the frame part is 0.01 to 1.0 times the thickness of the frame part, and a coating film containing a low-hydrophilic material formed on the one of its main surfaces.
  • the method for producing a water-repellent film of the present invention includes a ceramic slurry preparation step of preparing a ceramic slurry containing ceramic particles and an organic substance, a ceramic slurry film formation step of applying the ceramic slurry to a substrate to form a ceramic slurry film, a condensation step of blowing high humidity air onto one main surface of the ceramic slurry film that is not in contact with the substrate to condense water droplets on the one main surface of the ceramic slurry film and grow the water droplets to form multiple water droplet-shaped recesses on the one main surface of the ceramic slurry film, an evaporation step of heating the ceramic slurry film to evaporate the water droplets, a firing step of firing the ceramic slurry film at a temperature equal to or higher than the temperature at which the organic substance decomposes and sintering the ceramic particles to obtain a concave-convex structure made of a porous ceramic sintered body and including a film-shaped frame part having multiple water droplet-shaped recesses
  • the present invention provides a water-repellent film that can be easily manufactured at low cost and has a sufficiently high strength, as well as a method for manufacturing the water-repellent film.
  • FIG. 1A is a perspective view that illustrates an example of a water-repellent film of the present invention.
  • FIG. 1B is a cross-sectional view of the water-repellent film shown in FIG. 1A taken along line AA.
  • FIG. 2 is a cross-sectional view showing an example of a state in which a water droplet comes into contact with the water-repellent film of the present invention.
  • FIG. 3A is a plan view of the main surface of the frame portion of the concave-convex structure constituting the water-repellent film of the present invention, on the side where concave portions are formed.
  • FIG. 3B is a cross-sectional view taken along the line BB of the concave-convex structure shown in FIG. 3A.
  • FIG. 3C is a partially enlarged view of the cross section of the concave-convex structure shown in FIG. 3A taken along line CC.
  • FIG. 4A is a cross-sectional view that illustrates an example of a drop-shaped recess in the water-repellent film of the present invention.
  • FIG. 4B is a cross-sectional view that illustrates an example of a drop-shaped recess in the water-repellent film of the present invention.
  • FIG. 5 is a cross-sectional view that illustrates an example of the water-repellent film of the present invention, in which a coating film is formed on a portion other than one of the main surfaces of a frame portion.
  • FIG. 4A is a cross-sectional view that illustrates an example of a drop-shaped recess in the water-repellent film of the present invention.
  • FIG. 4B is a cross-sectional view that illustrates an example of a drop-shaped recess in the water-repellent film of the
  • FIG. 6 is a cross-sectional view that illustrates a schematic diagram of another example of the water-repellent film of the present invention.
  • FIG. 7 is a cross-sectional view that illustrates an example of the ceramic slurry film forming step in the method for producing a water-repellent film of the present invention.
  • FIG. 8A is a cross-sectional view that illustrates an example of a high humidity air blowing sub-step in the condensation process in the method for producing a water-repellent film of the present invention.
  • FIG. 8B is a cross-sectional view that illustrates an example of a water droplet growth sub-step in the condensation process in the method for producing a water-repellent film of the present invention.
  • FIG. 9 is a cross-sectional view that illustrates an example of the evaporation step in the method for producing a water-repellent film of the present invention.
  • FIG. 10 is a cross-sectional view that illustrates an example of a baking step in the method for producing a water-repellent film of the present invention.
  • FIG. 11 is a cross-sectional view that illustrates an example of a coating film forming step in the method for producing a water-repellent film of the present invention.
  • the present invention is not limited to the following configurations, and can be appropriately modified and applied within the scope of the present invention.
  • the present invention also includes a combination of two or more of the individual preferable configurations of the present invention described below.
  • terms indicating the relationship between elements e.g., "perpendicular,” “parallel,” “orthogonal,” etc.
  • terms indicating the shapes of elements are not expressions that express only a strict meaning, but are expressions that include a range of substantial equivalence, for example, differences of about a few percent.
  • the water-repellent film of the present invention comprises a film-like frame portion having a plurality of water-droplet-shaped recesses formed on one of its main surfaces, the frame portion being a porous ceramic sintered body, a concave-convex structure in which the average maximum depth of the recesses in the thickness direction of the frame portion is 0.01 to 1.0 times the thickness of the frame portion, and a coating film containing a low hydrophilic material formed on the one of its main surfaces.
  • the water-repellent film of the present invention may include any configuration as long as the above-mentioned configuration is satisfied and the effects of the present invention are achieved.
  • FIG. 1A is a perspective view that illustrates an example of a water-repellent film of the present invention.
  • FIG. 1B is a cross-sectional view of the water-repellent film shown in FIG. 1A taken along line AA.
  • the water-repellent film 1 shown in Figures 1A and 1B is composed of a concave-convex structure 2 including a film-like frame portion 20 having a plurality of droplet-shaped recesses 10 formed on one main surface 20a, and a coating film 3 containing a low-hydrophilic material formed on one main surface 20a of the frame portion 20.
  • the main surface 1a of the water-repellent film 1 on the side on which the coating film 3 is formed is the surface that exhibits water repellency.
  • a case where a water droplet comes into contact with the main surface 1a of the water-repellent film 1 will be described with reference to the drawings.
  • FIG. 2 is a cross-sectional view showing an example of a state in which a water droplet comes into contact with the water-repellent film of the present invention.
  • a water droplet W comes into contact with the main surface 1 a of the water-repellent film 1
  • the water droplet W comes into contact with the coating film 3 formed on one main surface 20 a of the frame portion 20 . Since the coating film 3 contains a low-hydrophilic material, the water droplets W are easily repelled.
  • a recess 10 is formed on one of the main surfaces 20a of the frame portion 20, and air is present in the recess 10. Therefore, the water droplet W does not come into contact with a flat surface, but rather comes into contact with an uneven surface consisting of the air and the frame portion 20. When the water droplet W comes into contact with such an uneven surface, the water droplet W is easily repelled.
  • the water-repellent film 1 exhibits high water repellency.
  • the contact angle with pure water on the main surface of the water-repellent film on the side on which the coating film is formed is preferably 90° or more, and more preferably 120° or more.
  • the contact angle with respect to pure water being in the above range means that the water-repellent film of the present invention has sufficiently high water repellency.
  • the contact angle with respect to pure water is measured according to JIS R 3257.
  • the concave-convex structure 2 and coating film 3 that make up the water-repellent film 1 are described in detail below.
  • the concave-convex structure 2 of the water-repellent film 1 includes a film-like frame portion 20 having a plurality of water-droplet-shaped recesses 10 formed on one main surface 20a.
  • the frame portion 20 is a porous ceramic sintered body.
  • the frame portion 20 may be made of only a porous ceramic sintered body. Moreover, it is preferable that the frame portion 20 does not contain any organic matter.
  • the porosity of the frame portion 20 is preferably 45% or less, and more preferably 0.1% or more and 20% or less. If the porosity of the frame portion 20 is 45% or less, the strength of the frame portion 20 is increased, and as a result, the water-repellent film 1 is less likely to be damaged. In addition, the frame portion 20 is also more resistant to external forces such as rubbing.
  • the "porosity of the frame portion” refers to the ratio of pores in the porous ceramic sintered body portion, and recesses are not taken into consideration when calculating the "porosity of the frame portion". In this specification, the "porosity of the frame portion" refers to a value measured by the following method.
  • the water-repellent film of the present invention is cut, and a scanning electron microscope (SEM) image of the cross section in an area of 1 ⁇ m ⁇ 1 ⁇ m is obtained.
  • SEM image is binarized to black and white, the part where the ceramic sintered body is present and the pore part are distinguished, and the number of pixels in each part is measured.
  • the ratio of the number of pixels in the pore part to the total number of pixels in the part where the ceramic sintered body is present and the pore part is calculated. The above value is calculated at any 10 points, and the average value is defined as the "void ratio of the frame portion.”
  • the hardness of the frame portion 20 is preferably 0.5 GPa or more and 30.0 GPa or less.
  • the hardness of the frame portion 20 falling within the above range means that the porous ceramic sintered body has been sufficiently sintered at high temperature.
  • the "hardness of the frame portion” refers to a value measured using a Nano Intender (product name: NET-1100a, manufacturer: Elionix Co., Ltd.).
  • FIG. 3A is a plan view of the main surface of the frame portion of the concave-convex structure constituting the water-repellent film of the present invention, on the side where concave portions are formed.
  • the multiple recesses 10 are aligned in a honeycomb pattern.
  • the recesses 10 are aligned in a honeycomb pattern, the difference in physical properties between different parts of the water-repellent film 1 becomes small, and the water-repellent film 1 has uniform properties.
  • the recesses 10 are formed by condensing water droplets when manufacturing the concave-convex structure 2. When the recesses 10 are formed in this manner, the recesses 10 are aligned in a honeycomb pattern.
  • the recesses are aligned in a honeycomb pattern means that the recesses are arranged in a honeycomb pattern at a constant interval and pattern.
  • constant interval and pattern refers not only to exactly the same interval and pattern, but also to cases where the interval between the recesses varies or the pattern of the recesses is misaligned.
  • the shape of the recess 10 when one of the main surfaces 20a of the frame portion 20 is viewed in plan view is circular, but in the water-repellent film of the present invention, the shape of the recess does not have to be a perfect circle and may be distorted.
  • the average value of the minimum length of the frame portion 20 located between adjacent recesses 10 is smaller than the average circular equivalent diameter of the recesses 10 (the average value of the circular equivalent diameters of the parts indicated by the symbol "S 1 " in Figure 3A).
  • the average value of the length L is preferably 0.01 ⁇ m or more and 10 ⁇ m or less.
  • the average equivalent circle diameter of the recesses 10 is preferably 0.1 ⁇ m or more and 100 ⁇ m or less.
  • the average value of the length L is smaller than the average equivalent circle diameter of the recesses 10 suggests that the walls forming the recesses 10 in the protrusion-recess structure 2 are thin, making the recesses 10 more susceptible to defects.
  • the frame portion 20 is made of a porous ceramic sintered body and is therefore highly hard, so that even if the wall portion constituting the recess 10 is thin, defects are unlikely to occur in the recess 10.
  • the average value of the length L being smaller than the average equivalent circle diameter of the recesses 10 means that the frame portion 20 is narrower, and with such a structure, the water repellency of the water-repellent film 1 is improved.
  • FIG. 3B is a cross-sectional view taken along the line BB of the concave-convex structure shown in FIG. 3A.
  • Figure 3B is a cross-sectional view of the concave-convex structure 2 cut so as to pass through the center of gravity of each recess 10 and be parallel to the thickness direction of the concave-convex structure 2 when one of the main surfaces 20a of the concave-convex structure 2 is viewed in a plane.
  • adjacent recesses 10 are partially in contact with each other and connected to each other.
  • the average value of the maximum depth of the recess 10 (the distance indicated by the symbol "D" in Figure 3B) in the thickness direction of the frame portion 20 (the direction indicated by arrow A in Figure 3B) is 0.01 to 1.0 times the thickness T of the frame portion 20.
  • the average value of the maximum depth D of the recess 10 is preferably 0.05 to 1.0 times the thickness T of the frame portion 20, and more preferably 0.1 to 1.0 times. If the average value of the maximum depth D of the recesses 10 is within the above range, it seems that the recesses 10 are formed deep and the concave-convex structure 2 is easily damaged.
  • the frame portion 20 is a porous ceramic sintered body and therefore has high hardness. Therefore, even if the recesses 10 are formed deep in this way, the concave-convex structure 2 is not easily damaged.
  • the maximum depth D of the recesses 10 is 1.0 times the thickness T of the frame portion 20, this means that the recesses 10 penetrate from one main surface 20a to the other main surface 20b of the frame portion 20.
  • the average value of the maximum depth D of the recesses 10 is 1.0 times the thickness T of the frame portion 20, this means that all the recesses 10 in the frame portion 20 penetrate from one main surface 20a to the other main surface 20b of the frame portion 20.
  • the average maximum depth D of the recesses 10 is preferably 0.1 ⁇ m or more and 100 ⁇ m or less, and more preferably 0.3 ⁇ m or more and 10 ⁇ m or less.
  • the thickness T of the frame portion 20 is preferably 0.3 ⁇ m or more and 10 ⁇ m or less.
  • the "thickness of the frame portion” means the maximum thickness of the frame portion.
  • the "average value of the maximum depth of the recesses” means a distance measured by the following method. First, the imaginary plane ⁇ is disposed so as to overlap exactly with one of the main surfaces 20a of the frame portion 20. The longest distance when a perpendicular line is drawn from the bottom surface of each recess to the imaginary plane ⁇ is defined as the “maximum depth of each recess.” The average value of the maximum depths of the recesses thus measured is the "average maximum depth of the recesses.”
  • the ratio of the area occupied by the recess 10 to the total area occupied by the frame portion 20 and the area occupied by the recess 10 is preferably 40% or more, and more preferably 60% or more and 90% or less. If the ratio of the area occupied by the recess 10 to the total area occupied by the frame portion 20 and the area occupied by the recess 10 is 40% or more, it seems that the recess 10 accounts for a large proportion of the uneven structure 2, and that the uneven structure 2 is prone to damage.
  • the frame portion 20 is a porous ceramic sintered body and has high hardness.
  • the term "area occupied by the recesses” means an area measured by the following method.
  • the imaginary plane ⁇ is disposed so as to overlap exactly with one main surface 20a of the frame portion 20.
  • the area of the portion surrounded by the imaginary plane ⁇ and the wall surface 11 of the recess 10 is the "area of the recess in a cross section parallel to the thickness direction of the concave-convex structure.”
  • FIG. 3C is a partially enlarged view of the cross section of the concave-convex structure shown in FIG. 3A taken along line CC.
  • the recess 10 in a cross section in the thickness direction of the protrusion-recess structure 2, the recess 10 has a portion where the contour is continuous without interruption.
  • the droplet-shaped recesses 10 in the concave-convex structure 2 can be formed by water droplets caused by condensation in the method for producing a water-repellent film of the present invention, as described below.
  • the term "droplet-shaped recess” refers to a recess having the following characteristics.
  • the drop-shaped recess 10 has a wall surface 11 that includes a curved surface.
  • the drop-shaped recess 10 has a maximum portion 12 where the distance of the imaginary line enclosed by the recess 10 becomes maximum when a virtual line perpendicular to the thickness direction A is moved from one main surface 20a to the other main surface 20b.
  • the drop-shaped recess 10 gradually narrows from the maximum portion 12 toward the other main surface 20b.
  • FIGS. 4A and 4B are cross-sectional views that diagrammatically show examples of droplet-shaped recesses in the water-repellent film of the present invention.
  • the recess 10A has a wall surface 11A that includes a curved surface.
  • the maximum portion 12A is located between one main surface 20a and the other main surface 20b.
  • the recess 10A widens from the opening 13A toward the maximum portion 12A and gradually narrows from the maximum portion 12A toward the other main surface 20b.
  • the wall surface 11B of the recess 10B includes a curved surface.
  • the maximum portion 12B is located at the opening 13B of the recess 10 (i.e., one of the main surfaces 20a).
  • the recess 10B gradually narrows from the maximum portion 12B toward the other main surface 20b.
  • the frame portion 20 may be a porous ceramic sintered body made of an oxide ceramic or non-oxide ceramic material.
  • oxide ceramics include aluminum oxide, zinc oxide, zirconium oxide, silicon oxide, yttrium oxide, lead zirconate titanate, barium titanate, iron oxide, magnesium oxide, strontium titanate, cobalt oxide, nickel oxide, manganese oxide, forsterite, steatite, and cordierite.
  • non-oxide ceramics include carbide ceramics such as titanium carbide, silicon carbide, boron carbide, and tungsten carbide; nitride ceramics such as silicon nitride, aluminum nitride, and titanium nitride; hydroxide ceramics such as hydroxyapatite; boride ceramics such as calcium boride, titanium boride, zirconium boride, vanadium boride, niobium boride, tantalum boride, chromium boride, molybdenum boride, tungsten boride, lanthanum boride, and hafnium boride; and silicide ceramics such as iron silicide, titanium silicide, zirconium silicide, niobium silicide, tantalum silicide, chromium silicide, molybdenum silicide, tungsten silicide, and hafnium silicide.
  • carbide ceramics such as titanium carbide
  • the frame portion 20 is a porous ceramic sintered body made of these materials, the hardness of the frame portion is increased, and the water-repellent film 1 is less likely to be damaged. It is preferable that the material of the frame portion 20 is appropriately determined according to the application of the water-repellent film 1 .
  • the coating film 3 contains a low hydrophilic material.
  • the term "low hydrophilic material” refers to a material that is used to form a film having a smooth surface with a surface roughness Ra of 0.1 ⁇ m or less, and that, when the contact angle of the smooth surface with pure water is measured, is 60° or more.
  • the contact angle with respect to pure water means a value measured in accordance with JIS R 3257.
  • the coating film 3 is preferably made of a material whose smooth surface has a contact angle with pure water of 60° or more, and more preferably 90° or more.
  • the low hydrophilic material may contain a compound having at least one functional group selected from the group consisting of a hydrocarbon group, a hydrogen fluoride group, and a silicone group. Since these functional groups exhibit hydrophobicity, when the coating film 3 is formed from such a low-hydrophilic material, the water repellency of the water-repellent film 1 is improved.
  • the low-hydrophilic material may include organic and inorganic materials.
  • the organic material may be a hydrophobic polymer.
  • Hydrophobic polymers include polystyrene, polyethylene, polypropylene, polysulfone, polybutadiene, and the like.
  • inorganic materials include metals and hydrophobic ceramics.
  • metals include chromium, copper, titanium, silver, platinum, gold, and aluminum.
  • the thickness of the coating film 3 is preferably 0.5 nm or more, and more preferably 1 to 10 nm.
  • the coating film 3 is formed on one main surface 20 a of the frame portion 20 .
  • the coating film may be formed on a portion other than one of the main surfaces of the frame part.
  • the coating film 3 may be formed on the inner wall of the recess 10.
  • FIG. 5 is a cross-sectional view that illustrates an example of the water-repellent film of the present invention, in which a coating film is formed on a portion other than one of the main surfaces of a frame portion.
  • the coating film of the present invention may also be formed on the side surface of the frame portion (not shown).
  • the coating layer is formed by a sputtering method or a dipping method. When the coating layer is formed by such a method, the coating layer is also formed on the inner wall of the recess.
  • FIG. 6 is a cross-sectional view that illustrates a schematic diagram of another example of the water-repellent film of the present invention.
  • the water-repellent film 101 shown in Figure 6 consists of a protrusion-recess structure 102 consisting of a frame portion 120 in which a recess 110 is formed, and a coating film 103 containing a low hydrophilic material formed on one main surface 120a of the frame portion 120.
  • a fine convex structure 130 is formed on the surface of the frame portion 120 .
  • Such a convex structure 130 is formed when the ceramic particles are sintered.
  • the formation of such convex structures 130 can increase the surface area of one main surface 120a of frame portion 120. Since coating film 103 is formed on one main surface 120a of frame portion 120, the water repellency of one main surface 120a of frame portion 120 is increased.
  • the average value of the minimum length L of the frame portion 120 located between adjacent recesses 110 is greater than the average height of the fine convex structures 130.
  • the average height of the fine convex structure 130 is preferably 0.01 ⁇ m or more and 1 ⁇ m or less.
  • the "average height of the fine convex structures" refers to a value measured by the following method. First, an image of the cross section of the frame part is obtained using a laser microscope or a scanning electron microscope (SEM) by FIB (Focused Ion Beam) or mechanical polishing, etc.
  • the outline of the frame part is identified based on the obtained image, and the arithmetic mean roughness (Ra) calculated according to JIS B 0601:2013 using image analysis software WinROOF (manufactured by Mitani Shoji) is the average height of the fine convex structure.
  • Ra arithmetic mean roughness
  • the water-repellent film of the present invention is useful for applications such as anti-reflection films, culture scaffolds, battery materials, oil-resistant films, inkjet liquid ejection heads, and building exterior walls.
  • the method for producing a water-repellent film of the present invention includes a ceramics slurry preparation step, a ceramics slurry film formation step, a condensation step, an evaporation step, a firing step, and a coating film formation step. Each step is described in detail below.
  • Ceramic particles and an organic substance are mixed to prepare a ceramic slurry.
  • the ceramic particles are preferably made of oxide ceramics or non-oxide ceramics.
  • oxide ceramics include aluminum oxide, zinc oxide, zirconium oxide, silicon oxide, yttrium oxide, lead zirconate titanate, barium titanate, iron oxide, magnesium oxide, strontium titanate, cobalt oxide, nickel oxide, manganese oxide, forsterite, steatite, cordierite, and the like.
  • non-oxide ceramics examples include carbide ceramics such as titanium carbide, silicon carbide, boron carbide, and tungsten carbide, and nitride ceramics such as silicon nitride, aluminum nitride, and titanium nitride.
  • boride ceramics such as calcium boride, titanium boride, zirconium boride, vanadium boride, niobium boride, tantalum boride, chromium boride, molybdenum boride, tungsten boride, lanthanum boride, and hafnium boride; and silicide ceramics such as iron silicide, titanium silicide, zirconium silicide, niobium silicide, tantalum silicide, chromium silicide, molybdenum silicide, tungsten silicide, and hafnium silicide.
  • the average particle size of the ceramic particles is preferably 1/10 or less, and more preferably 1/100 or less, of the average value of the maximum depth of the recesses in the thickness direction of the frame portion obtained through the process described below.
  • the average particle size of the ceramic particles is preferably 0.01 ⁇ m or more and 1 ⁇ m or less.
  • Organic substances include surfactants, dispersion stabilizers, resin polymers, and organic solvents.
  • the ceramic slurry contains a surfactant, it becomes easier to form uniform recesses in the condensation step described below.
  • a surfactant an amphiphilic compound having both a hydrophilic group and a hydrophobic group, such as amphiphilic polyacrylamide or lecithin, can be used.
  • the ceramic particles can be suitably dispersed.
  • the dispersion stabilizer that can be used include methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, aminomethyl hydroxypropyl cellulose, aminoethyl hydroxypropyl cellulose, starch, tragacanth, pectin, glue, alginic acid or a salt thereof, gelatin, polyvinylpyrrolidone, polyacrylic acid or a salt thereof, polymethacrylic acid or a salt thereof, polyacrylamide, polymethacrylamide, copolymers of vinyl acetate and unsaturated acids such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and crotonic acid, copolymers of styrene and the above
  • the organic solvent that can be used includes water-immiscible organic solvents such as carbon tetrachloride, dichloromethane, chloroform, benzene, toluene, xylene, ethyl acetate, butyl acetate, methyl isobutyl ketone, and carbon disulfide.
  • water-immiscible organic solvents such as carbon tetrachloride, dichloromethane, chloroform, benzene, toluene, xylene, ethyl acetate, butyl acetate, methyl isobutyl ketone, and carbon disulfide.
  • the mass ratio of the ceramic particles contained in the ceramic slurry is preferably 70 mass % or more and 95 mass % or less. Within such a range, the recesses are less likely to collapse when they are formed in the condensation step described below, and the ceramic particles can be reliably sintered together in the firing step described below.
  • FIG. 7 is a cross-sectional view that illustrates an example of the ceramic slurry film forming step in the method for producing a water-repellent film of the present invention.
  • the ceramic slurry is applied to the substrate 40 to form a ceramic slurry film 20'.
  • FIG. 8A is a cross-sectional view that illustrates an example of a high humidity air blowing sub-step in the condensation process in the method for producing a water-repellent film of the present invention.
  • FIG. 8B is a cross-sectional view that illustrates an example of a water droplet growth sub-step in the condensation process in the method for producing a water-repellent film of the present invention.
  • high-humidity air 50 is blown onto one of the main surfaces 20a' of the ceramic slurry film 20' that is not in contact with the substrate 40, causing water droplets 60 to condense on the one of the main surfaces 20a' of the ceramic slurry film 20'.
  • the humidity of the high humidity air 50 is preferably 80% or more and 90% or less.
  • the temperature of the high humidity air 50 is preferably 10°C or higher and 40°C or lower.
  • the flow velocity when the high humidity air 50 is blown is preferably 0.1 m/s or more and 20 m/s or less.
  • ⁇ Water droplet growth sub-step> Next, as shown in Fig. 8B, the water droplets 60 are grown by continuing to supply high humidity air 50.
  • the water droplets 60 come into contact with each other and are arranged in a certain pattern due to the action of capillary force, etc.
  • a plurality of water droplet-shaped recesses 10' can be formed on one of the main surfaces 20a'.
  • the density, size, etc. of the recesses 10 ′ can be controlled by adjusting the humidity, temperature, flow velocity, flow rate, blowing angle, supply time, etc. of the high humidity air 50 .
  • the organic solvent component contained in the slurry volatilizes.
  • the recesses 10' can be formed easily and at low cost.
  • the water-repellent film produced through the subsequent processes can also be produced easily and at low cost.
  • FIG. 9 is a cross-sectional view that illustrates an example of the evaporation step in the method for producing a water-repellent film of the present invention.
  • the ceramic slurry film 20' on which the water droplets 60 have condensed is heated to evaporate the water droplets 60.
  • the heating conditions are not particularly limited as long as the water droplets 60 can evaporate.
  • the heating conditions include a temperature of 20° C. or higher and 40° C. or lower, a time of 1 minute to 60 minutes, and an atmospheric humidity of 60% or lower.
  • FIG. 10 is a cross-sectional view that illustrates an example of a baking step in the method for producing a water-repellent film of the present invention.
  • the ceramic slurry film 20' is fired at a temperature equal to or higher than the decomposition temperature of the organic matter to sinter the ceramic particles.
  • the organic matter in the ceramic slurry film 20' is decomposed, and the ceramic particles are sufficiently sintered together.
  • the ceramic slurry film 20' and the recess 10' become the frame portion 20 and the recess 10, respectively.
  • a protrusion-recess structure 2 which is made of a porous ceramic sintered body and has a membrane-like frame portion 20 on one main surface 20a thereof, on which a plurality of water droplet-shaped recesses 10 are formed.
  • firing is preferably performed under conditions in which the porosity of the porous ceramic sintered body constituting the frame portion is 45% or less. Examples of such firing conditions include a method in which the temperature is increased in an air atmosphere at a rate of 0.1° C./min to 50° C./min to a temperature of 1000° C. to 1600° C., and the temperature is maintained at this temperature for 1 min to 1440 min.
  • the evaporation process and the baking process may be carried out consecutively or separately.
  • FIG. 11 is a cross-sectional view that illustrates an example of a coating film forming step in the method for producing a water-repellent film of the present invention.
  • a coating film 3 containing a low-hydrophilic material is formed on one main surface 20 a of the frame portion 20 .
  • the preferred low hydrophilic materials are as described above, so a detailed explanation will be omitted here.
  • Examples of methods for forming the coating film 3 include a coating method, a dipping method, a sputtering method, a vapor deposition method, a spray coating method, and a spin coating method. It is preferable that these methods are appropriately selected depending on the type of low hydrophilic material.
  • the coating film 3 when the coating film 3 is formed using a hydrophobic polymer as the low hydrophilic material, it is preferable to employ a coating method or a dipping method.
  • a coating method or a dipping method when forming the coating film 3 using at least one metal selected from the group consisting of chromium, copper, titanium, silver, platinum, gold and aluminum as a low hydrophilic material, it is preferable to adopt a sputtering method or a vapor deposition method.
  • the ceramic slurry preparation process it is preferable to carry out the ceramic slurry preparation process, ceramic slurry film forming and configuring process, condensation process, evaporation process, and firing process so that the average maximum depth of the recesses in the thickness direction of the frame part is at least 0.01 times and less than 1.0 times the thickness of the frame part.
  • the average maximum depth of the recesses can be controlled by adjusting the composition of the ceramic slurry, the thickness of the ceramic slurry film, the conditions for condensing water droplets, and the firing conditions.
  • the thickness of the frame portion can be controlled by adjusting the composition of the ceramic slurry, the thickness of the ceramic slurry film, the heating conditions in the evaporation step, and the firing conditions.
  • the surface that exhibits water repellency is the surface on which the coating film is formed. Therefore, in the water-repellent film of the present invention, as long as one main surface of the frame portion exists, the other portion of the frame portion may not be present. Therefore, depending on the application of the water-repellent film, one main surface of the frame portion may be left and the other portion of the frame portion may be cut.
  • the cutting direction may be perpendicular to the thickness direction of the frame portion. Furthermore, the cutting may result in a structure in which the recess penetrates from one main surface of the frame portion to the other main surface (i.e., the cut surface).
  • the cutting may be performed between the ⁇ firing step> and the ⁇ coating film forming step>, or may be performed after the ⁇ coating film forming step>.
  • the present disclosure (1) is a water-repellent film consisting of a concave-convex structure comprising a film-like frame part having a plurality of droplet-shaped recesses formed on one of its main surfaces, the frame part being a porous ceramic sintered body, the average maximum depth of the recesses in the thickness direction of the frame part being 0.01 to 1.0 times the thickness of the frame part, and a coating film containing a low-hydrophilic material formed on the one of its main surfaces.
  • the present disclosure (2) is the water-repellent film described in the present disclosure (1), in which the porosity of the frame portion is 45% or less.
  • the present disclosure (3) is a water-repellent film according to the present disclosure (1) or (2), in which the average maximum depth of the recess in the thickness direction of the frame portion is 0.1 ⁇ m or more and 100 ⁇ m or less.
  • the present disclosure (4) is a water-repellent film according to any one of the present disclosures (1) to (3), in which the recesses are aligned in a honeycomb pattern when the one main surface of the frame portion is viewed in a plan view.
  • the present disclosure (5) is a water-repellent film according to any one of the present disclosures (1) to (4), in which, in a cross section parallel to the thickness direction of the water-repellent film, the ratio of the area occupied by the recess to the total area occupied by the frame portion and the recess is 40% or more.
  • the present disclosure (6) relates to a method for manufacturing the frame portion, comprising the steps of: aluminum oxide, zinc oxide, zirconium oxide, silicon oxide, yttrium oxide, lead zirconate titanate, barium titanate, iron oxide, magnesium oxide, strontium titanate, cobalt oxide, nickel oxide, manganese oxide, forsterite, steatite, cordierite, titanium carbide, silicon carbide, boron carbide, tungsten carbide, silicon nitride, aluminum nitride, titanium nitride, hydroxyapatite, calcium boride, boride
  • the water-repellent film according to any one of disclosures (1) to (5) is a porous ceramic sintered body made of at least one material selected from the group consisting of titanium, zirconium boride, vanadium boride, niobium boride, tantalum boride, chromium boride, molybdenum boride, tungsten boride, lan
  • the present disclosure (7) is a water-repellent film according to any one of the present disclosures (1) to (6), in which, when the one of the main surfaces of the frame portion is viewed in plan, the average value of the minimum length of the frame portion located between the adjacent recesses is smaller than the average value of the circle-equivalent diameter of the recesses.
  • the present disclosure (8) is a water-repellent film according to any one of the present disclosures (1) to (7), in which a fine convex structure is formed on the surface of the frame portion.
  • the present disclosure (9) is a water-repellent film according to the present disclosure (8), in which, when the one of the main surfaces of the frame portion is viewed in plan, the average value of the minimum length of the frame portion located between the adjacent recesses is greater than the average height of the fine convex structure.
  • the present disclosure (10) is a water-repellent film according to any one of the present disclosures (1) to (9), in which the thickness of the coating film is 0.5 nm or more.
  • the present disclosure (11) is a water-repellent film according to any one of the present disclosures (1) to (10), in which the coating film is made of a material that has a contact angle of 60° or more with pure water on a smooth surface.
  • the present disclosure (12) is a water-repellent film according to any one of the present disclosures (1) to (11), in which the coating film has at least one functional group selected from the group consisting of a hydrocarbon group, a hydrogen fluoride group, and a silicone group.
  • the present disclosure (13) is a water-repellent film according to any one of the present disclosures (1) to (12), in which the coating film contains a hydrophobic polymer.
  • the present disclosure (14) is a water-repellent film according to any one of the present disclosures (1) to (11), in which the coating film contains at least one metal selected from the group consisting of chromium, copper, titanium, silver, platinum, gold, and aluminum.
  • the present disclosure is a method for producing a water-repellent film, which includes a ceramic slurry preparation step of preparing a ceramic slurry containing ceramic particles and an organic substance, a ceramic slurry film formation step of applying the ceramic slurry to a substrate to form a ceramic slurry film, a condensation step of blowing high-humidity air onto one main surface of the ceramic slurry film that is not in contact with the substrate, condensing water droplets on the one main surface of the ceramic slurry film, and growing the water droplets to form multiple water droplet-shaped recesses on the one main surface of the ceramic slurry film, an evaporation step of heating the ceramic slurry film to evaporate the water droplets, a firing step of firing the ceramic slurry film at a temperature equal to or higher than the temperature at which the organic substance decomposes, and sintering the ceramic particles to obtain a concave-convex structure made of a porous ceramic sintered body and including a film-shaped frame
  • the present disclosure (16) is a method for producing a water-repellent film according to the present disclosure (15), which includes carrying out the ceramic slurry preparation process, the ceramic slurry film forming and constructing process, the condensation process, the evaporation process, and the firing process so that the average maximum depth of the recesses in the thickness direction of the frame portion is 0.01 to 1.0 times the thickness of the frame portion.
  • Al 2 O 3 nanopowder average particle size: 0.2 ⁇ m, product name: AKP-50, manufacturer: Sumitomo Chemical Co., Ltd.
  • ⁇ Ceramics slurry film formation process The ceramic slurry was applied to a heat-resistant base material (alumina substrate) to form a ceramic slurry film having a thickness of 500 ⁇ m.
  • the ceramic slurry film was heated in a sintering furnace in an air atmosphere at a temperature increase rate of 20°C/min up to 1400°C and held at that temperature for 60 minutes to decompose the organic matter and sinter the ceramic particles together to form a porous ceramic sintered body.
  • a film-like frame part having a plurality of waterdrop-shaped recesses formed on one main surface was obtained.
  • the water-repellent film according to Example 1 was manufactured.
  • the porosity of the porous ceramic sintered body was 4%.
  • the hardness of the frame portion measured with a nanointender (product name: NET-1100a, manufacturer: Elionix Co., Ltd.) was 18.5 GPa.
  • the average minimum length of the frame portion located between adjacent recesses was 0.7 ⁇ m, and the average circular equivalent diameter of the recesses was 3.3 ⁇ m.
  • the thickness of the frame portion was 11 ⁇ m, and the average maximum depth of the recesses was 2.9 ⁇ m.
  • a fine convex structure was formed on the surface of the frame portion, and the height of the convex structure was 0.2 ⁇ m.
  • the coating film had a thickness of 10 nm.
  • platinum was sputtered onto another substrate to form a platinum film with a smooth surface and a surface roughness Ra of 0.005 ⁇ m.
  • the contact angle of the smooth surface of the platinum film with pure water was measured to be 72°.
  • Example 2 A water-repellent film according to Example 2 was formed in the same manner as in Example 1, except that the above-mentioned ⁇ coat film forming step> was changed to the following ⁇ coat film forming step'>.
  • the frame portion was immersed in a polystyrene resin solution prepared by dissolving polystyrene resin in a chloroform solution to a concentration of 1 g/L, and then pulled up at a speed of 1 mm/s to perform dip coating, followed by drying to form a coating film.
  • a polystyrene resin solution prepared by dissolving polystyrene resin in a chloroform solution to a concentration of 1 g/L, and then pulled up at a speed of 1 mm/s to perform dip coating, followed by drying to form a coating film.
  • the water-repellent film according to Example 2 was manufactured.
  • the porosity of the porous ceramic sintered body, the hardness of the frame portion, the shape of the recesses, and the structure of the fine convex structures formed on the surface of the frame portion were the same as those of the water-repellent film of Example 1.
  • the thickness of the coating film was 0.01 nm.
  • another substrate was immersed in the polystyrene resin solution dissolved in the above chloroform solution, and was then pulled up at a speed of 1 mm/s, followed by dip coating to form a polystyrene resin film having a smooth surface with a surface roughness Ra of 0.005 ⁇ m.
  • the contact angle of the smooth surface of the polystyrene resin film with pure water was measured to be 93°.
  • ⁇ Comparative Example 1> A water-repellent film according to Comparative Example 1 was formed in the same manner as in Example 1, except that the above-mentioned ⁇ condensation step> and the above-mentioned ⁇ evaporation step> were not carried out.
  • the water-repellent film in Comparative Example 1 is a water-repellent film in which a coating film made of platinum is formed on one main surface of a porous ceramic sintered body on which no recesses are formed.
  • ⁇ Comparative Example 2> A water-repellent film according to Comparative Example 2 was formed in the same manner as in Example 2, except that the above-mentioned ⁇ condensation step> and the above-mentioned ⁇ evaporation step> were not carried out.
  • the water-repellent film in Comparative Example 2 is a water-repellent film in which a coating film made of polystyrene resin is formed on one main surface of a porous ceramic sintered body on which no recesses are formed.
  • the water-repellent films of Examples 1 and 2 in which a coating film is formed on one of the main surfaces of the frame portion in which the recess is formed, were found to have higher water repellency than the water-repellent films of Comparative Examples 1 and 2, in which a coating film is formed on the smooth surface of the porous ceramic sintered body.

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  • Ceramic Engineering (AREA)
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  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

Sont divulgués : un film hydrofuge pouvant être fabriqué facilement à faible coût et présentant une résistance suffisamment élevée ; et un procédé de fabrication du film hydrofuge. Le film hydrofuge (1) selon la présente invention comprend une partie cadre en forme de film (20) comportant une pluralité d'évidements en forme de gouttelettes d'eau (10) formés dans une surface principale (20a) de celle-ci. La partie cadre (20) est un corps fritté en céramique poreuse et comprend : une structure saillante et évidée (2) dont la valeur moyenne des profondeurs maximales (D) des évidements (20) dans le sens de l'épaisseur de la partie cadre (20) est de 0,01 à 1,0 fois l'épaisseur de ladite partie (20) ; et un film de revêtement (3) contenant un matériau faiblement hydrophile et formé sur la surface principale (20a) de la partie cadre (20).
PCT/JP2023/036554 2023-02-24 2023-10-06 Film hydrofuge et procédé de fabrication dudit film Ceased WO2024176509A1 (fr)

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