EP2594343A2 - Matériau hydrophobe et son procédé de production - Google Patents

Matériau hydrophobe et son procédé de production Download PDF

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Publication number
EP2594343A2
EP2594343A2 EP12192414.6A EP12192414A EP2594343A2 EP 2594343 A2 EP2594343 A2 EP 2594343A2 EP 12192414 A EP12192414 A EP 12192414A EP 2594343 A2 EP2594343 A2 EP 2594343A2
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European Patent Office
Prior art keywords
substrate
fine uneven
hydrophobic
petal
uneven structure
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EP12192414.6A
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German (de)
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EP2594343A3 (fr
EP2594343B1 (fr
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Riichiro Ohta
Tomoyuki Koga
Takeshi Ohwaki
Atsuto Okamoto
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Toyota Central R&D Labs Inc
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Toyota Central R&D Labs Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/102—Pretreatment of metallic substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/60—Adding a layer before coating
    • B05D2350/63—Adding a layer before coating ceramic layer

Definitions

  • the present invention relates to a hydrophobic material and a production process thereof, and more particularly to a hydrophobic material in which a super hydrophobic layer having extremely high hydrophobicity is formed on a surface of a substrate, and a production process thereof.
  • Super hydrophobicity refers to a phenomenon that water droplets contact the surface of a material at a contact angle of 150° or more. When the surface of a material has super hydrophobicity, water droplets on the surface of the material become spherical and slide on the surface. It has been contemplated to apply a material including the super hydrophobicity to the body of a vehicle which requires the reduction in washing costs, the hull of a high speed vessel which requires the reduction in water friction, the external wall of a house which requires anti-contamination, rain gear or clothing which requires waterproof property, a heat exchanger or an antenna of a cold district, which requires the prevention of frost formation, and the like.
  • Patent Document 1 discloses a super hydrophobic aluminum foil with the coating film of a condensate of hexyltrimethoxysilane which does not include fluorine or a condensate of heptadecafluorodecyltrimethoxysilane which includes fluorine directly provided on the surface of the hot water-treated metal aluminum foil.
  • the document describes that:
  • Patent Document 2 discloses a scroll vacuum pump, in which (1) the surface of a fixed scroll and a rotary scroll consisting of aluminum casting is subjected to anodic oxidation treatment,
  • Patent Document 3 discloses a method of sputtering Al on a glass substrate to 140 nm thick, putting the glass substrate into ion exchanged water, and leaving the glass substrate to stand as it is at 90°C for 60 minutes. The document describes that a nanosheet structure is formed on the glass substrate by the method.
  • Non-Patent Document 1 which does not relate to a hydrophobic material, but discloses a method of immersing an yttria-stabilized tetragonal zirconia substrate in a suspension (70°C) which is prepared by dispersing an AlN powder in water, lifting the substrate after a predetermined time has elapsed, and drying the substrate.
  • a suspension 70°C which is prepared by dispersing an AlN powder in water, lifting the substrate after a predetermined time has elapsed, and drying the substrate.
  • a problem to be solved by the present invention is to provide a novel hydrophobic material provided with super hydrophobicity and a production process thereof.
  • the gist of the hydrophobic material according to the present invention is to include the following constitutions.
  • the gist of the production process of the hydrophobic material according to the present invention is to include the following constitutions.
  • a fine uneven structure including a fine petal-like structure and a coarse columnar structure may be formed.
  • the surface of the fine uneven structure is covered with a hydrophobic molecule, excellent super hydrophobicity is exhibited, compared to the case in which the surface of the substrate including only a fine petal-like structure is covered with a hydrophobic molecule. This is thought to be because the contact area between water droplets and a fine uneven structure decreases and the area of the interface between droplets and an air layer, which is formed between the projections increases, by combining the petal-like structure with the columnar structure.
  • the hydrophobic material according to the present invention includes the following constitutions:
  • the shape of the substrate is not particularly limited and may be arbitrarily selected according to the purpose.
  • Examples of the shape of the substrate include a plate, a rod, a tube, a honeycomb, a fiber, a foil, a powder, a porous body and the like.
  • the material for the substrate is not particularly limited, and an appropriate material may be selected according to the method of forming a fine uneven structure to be described below, the use of the hydrophobic material and the like.
  • Examples of the material for the substrate include:
  • an aluminum-containing material is preferably used as the substrate.
  • the "aluminum-containing material” refers to a material which includes Al as a significant component and may elute Al having an amount sufficient to precipitate boehmite and bayerite on the surface of the material by hot-water treatment under the coexistence of an amine-based molecule.
  • the aluminum-containing material include aluminum, an aluminum alloy, aluminum nitride, aluminum gallium nitride and the like.
  • a fine uneven structure is formed on the surface of a substrate.
  • the fine uneven structure may be formed on the entire surface of the substrate, or may be formed on only a portion which requires super hydrophobicity in the surface of a substrate.
  • the "fine uneven structure” refers to a structure including a fine petal-like structure and a coarse columnar structure.
  • the "petal-like structure” refers to a structure formed of an aggregate of a plurality of plate-like particles. Individual plate-like particles are facing random directions in the surface of the substrate. That is, the petal-like structure refers to a structure in which fine plate-like particles having a nanometer-sized thickness are densely packed like petals. The petal-like structure is formed in a region in which at least a columnar structure is not formed in the surface of the substrate. Further, according to the preparation method of the fine uneven structure, a petal-like structure may be further formed on the surface of the columnar structure in some cases.
  • the size of plate-like particles constituting the petal-like structure varies depending on the preparation method of the petal-like structure, but in order to obtain high hydrophobicity, the thickness of plate-like particles is preferably from 0.3 nm to 50 nm.
  • the "columnar structure” refers to a structure formed of columnar particles.
  • the length (L 1 ) from the surface of the substrate to the tip of the columnar structure needs to be longer than the length (L 2 ) from the surface of the substrate to the tip of the petal-like structure.
  • at least one end of the columnar structure needs to be at a position spaced apart from the tip of petal-like structure formed on the surface of the substrate. The bigger the difference between the size of the columnar structure and the size of the petal-like structure is, the higher the hydrophobicity becomes.
  • L 1 is longer than L 2 by preferably two-folds or more, more preferably five-folds or more, and even more preferably ten-folds or more.
  • the size of columnar particles constituting the columnar structure varies depending on the preparation method of the columnar structure, but in order to obtain high hydrophobicity, the columnar particles preferably have a diameter of 0.4 nm or more and a length of 50 nm or more.
  • the "diameter of columnar particles” refers to a maximum length of the cross-section in a vertical direction to the axis direction of columnar particles.
  • the columnar particles need not be a cylinder.
  • the diameter of the columnar particles refers to the diagonal length of the regular square.
  • the upper limit of the diameter of the columnar structure which may exhibit super hydrophobicity varies depending on the size of water droplets which contact the surface thereof. Even though the diameter of the columnar structure is large, when water droplets are sufficiently larger than the columnar structure, super hydrophobicity may be exhibited. For this reason, the diameter of the columnar structure may be appropriately adjusted depending on the size of water droplets to be a target in accordance with the use of the hydrophobic material. The number density of the columnar structure may also be appropriately optimized depending on the size of water droplets to be a target in accordance with the use of the hydrophobic material.
  • the columnar structure is bayerite and uses the preparation method of the present invention, it is technically difficult to obtain a columnar structure having a diameter of 1 mm or more.
  • the columnar structure is carbon, it is technically difficult to obtain a columnar structure formed of monolayered carbon nanotubes and having a diameter of 0.4 nm or less. Even when the length of the columnar structure is longer than necessary, there is no difference in obtaining super hydrophobicity, and thus there is no substantial advantage.
  • the columnar structure is bayerite and uses the method according to the present invention, it is technically difficult to obtain a columnar structure having a length of 1 mm or more.
  • coarse columnar particles having a size from submicron to micron are discretely formed on the surface of the substrate and a fine petal-like structure having a nanometer-size is formed in the gap thereof.
  • the columnar structure may be formed directly on the surface of the substrate in some cases, or may be formed on the petal-like structure to be a basis in some cases.
  • Individual columnar particles usually are facing random directions, and thus an angle formed by the axis direction of the columnar particles and the surface of the substrate varies for each particle. That is, there are columnar particles grown almost vertically to the surface of the substrate, and there are columnar particles grown almost in parallel to the surface of the substrate.
  • the material constituting the petal-like structure and the columnar structure is not particularly limited, and various materials may be used depending on the formation method thereof.
  • Examples of the material constituting the petal-like structure include boehmite, carbon, nickel hydroxide and the like.
  • Examples of the material constituting the columnar structure include bayerite, carbon and the like.
  • the combination of materials constituting the petal-like structure and the columnar structure is not particularly limited, and various combinations may be selected depending on the formation method thereof.
  • the petal-like structure is formed of boehmite and the columnar structure is formed of bayerite.
  • Examples of other material combinations include (carbon nanowall, carbon nanofiber), (carbon nanowall, carbon nanotube) and the like.
  • the hydrophobic molecule is a molecule including a polar functional group (B) to be described below
  • the polar functional group (B) has high adsorptivity to:
  • the surface of the fine uneven structure is covered with a hydrophobic molecule.
  • the hydrophobic molecule may be only physically adsorbed on the surface of the fine uneven structure in some cases, or may be chemically bonded to the surface of the fine uneven structure through the polar functional group (B) in some cases.
  • the "hydrophobic molecule” refers to a molecule in which when a flat surface is densely covered with the molecule and droplets are added dropwise thereto, an angle (static contact angle of water droplet) formed by the surface thereof and water droplets is 90° or more.
  • the hydrophobic molecule may be a molecule including only a moiety that contributes to hydrophobic property, or a molecule further including the polar functional group (B) that may form a chemical bond between the molecule and the surface of the fine uneven structure, in addition to the moiety.
  • the polar functional group (B) may only react with a metal oxide or the polar functional group (A) which is present on the surface of the fine uneven structure, and need not always be the same functional group as the polar functional group (A).
  • a hydrophobic molecule that does not include the polar functional group (B) may be physically adsorbed on the surface of a substrate to form a coating film when the molecule has a high molecular weight and exists as a solid around at room temperature.
  • the coating film has a weak interaction with the substrate, and thus the mechanical durability thereof is extremely low.
  • hydrophobicity may be sustained over a long period.
  • hydrophobic molecule molecules including a fluoroalkyl group (Rf) and molecules including a hydrocarbon group are known.
  • the hydrophobicity of a hydrophobic molecule including Rf is higher than that of a hydrophobic molecule including a hydrocarbon group.
  • the hydrophobic molecule including Rf has high hydrophobicity as the number of carbons in Rf increases.
  • examples of the polar functional group (B) include:
  • hydrophobic molecule examples include the followings. These hydrophobic molecules may be used either alone or in combination of two or more thereof.
  • a first specific example is a molecule represented by the following Formula (a) as a hydrophobic molecule including a silanol-based functional group.
  • R a monovalent hydrocarbon having from 1 to 8 carbon atoms
  • X -OR (R is an alkyl group), -OH or a halogen atom
  • l an integer of 0 or higher
  • m an integer from 1 to 5
  • n an integer from 0 to 2
  • a and b 2 or 3.
  • the molecular weight of a hydrophobic molecule represented by Formula (a) varies depending on the number of carbons of R or the number (l, m, n) of repetitions of the repeating unit, but is usually in a range from 2,000 to 3,000.
  • the molecule represented by Formula (a) is commercially available.
  • a second specific example is a molecule represented by the following Formula (b) as a hydrophobic molecule including a silanol-based functional group.
  • Formula (b) an integer from 1 to 10.
  • the hydrophobic molecule represented by Formula (b) exhibits hydrophobicity higher than that of the hydrophobic molecule represented by Formula (a).
  • the hydrophobic molecule represented by Formula (b) is commercially available.
  • a third specific example is a molecule including an Rf having 8 carbon atoms or more (hereinafter referred to as "hydrophobic molecule (c)”) as a hydrophobic molecule including a silanol-based functional group.
  • hydrophobic molecule (c) examples include (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trichlorosilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)-1-triethoxysilan e, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)-1-trimethoxysila ne and the like.
  • the hydrophobic molecule (c) has been frequently used until now in the preparation of a hydrophobic surface, in that a silanol-based functional group easily reacts with the surface of a substrate.
  • environmental pollution or toxicity to an animal or a human body caused by these molecules has become a problem.
  • (heptadecafluoro-1,1,2,2-tetrahydrodecyl)-1-triethoxysilan e causes damage to the lung (Reference Document 1).
  • Reference Document 1 " Lung Damage in Mice after Inhalation of Nanofilm Spray Products: The Role of Perfluorination and Pree Hydroxyl Groups," Asger W.Norggad, Soren T. Larsen, Maria Hammer, Steen S. Poulsen, Keld A. Jensen, Gunnar D.Nielsen, Peder Wolkoff; Toxicological Science 116(1),216-224(2010 ).
  • Reference Document 2 Report of the Persistent Organic Pollutants Review Committee on the work of its sixth meeting, Addendum, Guidance on alternatives to perfluorooctane sulfonate and its derivatives, 14 October 2011 .
  • Reference Document 3 Milijostyrelsen, Pressemeddelelser, Nanospray, 16 April 2010 .
  • PFOA perfluorooctanoic acid
  • molecules represented by Formulas (a) and (b) exhibit high hydrophobicity and do not generate molecules including an Rf having 8 carbon atoms or more even when these molecules are decomposed, and thus the bioaccumulation potential is low. For this reason, molecules represented by Formulas (a) and (b) are suitable as a hydrophobic molecule.
  • the molecules represented by Formulas (a) and (b) may be used either alone or in combination of two or more thereof.
  • the hydrophobic molecule including a silanol-based functional group may be prepared by using, as a raw material, an ethylene-based hydrophobic molecule that is a hydrophobic molecule having a carbon-carbon double bond, or an acetylene-based hydrophobic molecule that is a hydrophobic molecule having a carbon-carbon triple bond.
  • a hydrophobic molecule including a chlorosilane group may be prepared by reacting an ethylene-based hydrophobic molecule with trichlorosilane.
  • a hydrophobic molecule including a methoxysilane group may be prepared by reacting an ethylene-based hydrophobic molecule with trimethoxysilane.
  • a hydrophobic molecule including an ethoxysilane group may be prepared by reacting an ethylene-based hydrophobic molecule with triethoxysilane.
  • a platinum-based catalyst such as C 8 H 18 OSi 2 Pt (Karstedt catalyst), H 2 PtCl 6 (Speyer catalyst) and the like, a nickel-based catalyst, a palladium-based catalyst, a ruthenium-based catalyst, and the like may be used.
  • hydrophobic molecule including polar functional groups other than a silanol-based functional group include:
  • hydrophobic molecule which does not include a polar functional group
  • PFPE including a fluorocarbon group at both ends of the molecular chain thereof, and the like. These are commercially available or may be prepared by a known method using a compound having a similar molecular structure as a starting material.
  • the hydrophobic molecule may be a molecule that may only cover the surface of the fine uneven structure physically, or a molecule in which a chemical bond is formed between the surface of the fine uneven structure and the polar functional group (B). The method of forming the chemical bond will be described below.
  • the production process of the hydrophobic material according to the present invention includes a fine unevenness step and a covering step.
  • the production process of the hydrophobic material may further include a bonding step.
  • the unevenness step is a step of forming a fine uneven structure including a petal-like structure formed of an aggregate of a plurality of plate-like particles and a columnar structure formed of columnar particles on a surface of the substrate, in which a length from a surface of the substrate to a tip of the columnar structure is longer than a length from the surface of the substrate to a tip of the petal-like structure, thereby obtaining a fine uneven substrate.
  • the method of forming the fine uneven structure is not particularly limited, and an appropriate method may be selected according to the material constituting the substrate and the material constituting the fine uneven structure. Specific examples thereof include the following methods.
  • a first method is a method (hot-water treatment method) of immersing a substrate in a solution including water and an amine-based molecule at a temperature from 60°C to 300°C when the substrate is an aluminum-containing material.
  • a fine uneven structure including a petal-like structure formed of boehmite and a columnar structure formed of bayerite on the surface of the substrate formed of the aluminum-containing material.
  • amine-based molecule refers to:
  • the content of the amine-based molecule included in an aqueous solution is not particularly limited, and may be arbitrarily selected according to the purpose. In general, as the content of the amine-based molecule increases, a fine uneven structure may be formed by treatment at a lower temperature and/or for a shorter period.
  • the hot-water treatment temperature needs to be 60°C or more.
  • the hot-water treatment temperature is more preferably 80°C or more, and even more preferably 100°C or more.
  • the hot-water treatment temperature needs to be 300°C or less.
  • the time for the hot-water treatment is sufficient as long as it is time during which a desired fine uneven structure is formed.
  • the hot-water treatment temperature is increased, a fine uneven structure may be formed for a shorter period. Further, when the hot-water treatment temperature exceeds the boiling point of an aqueous solution, it is necessary to perform the hot-water treatment in a hermetically sealed container.
  • boehmite and bayerite are known to be formed during hydro-thermal sealing of an anodic oxidation coating film.
  • boehmite is formed by treatment at about 80°C or higher, while bayerite is formed by treatment at about 80°C or lower.
  • bayerite is formed at a temperature lower than that of boehmite, and it is presumed that boehmite is precipitated when kept at a high temperature, and then bayerite is precipitated during the cooling.
  • Both a petal-like structure and a columnar structure are formed by adding an amine-based molecule to a treatment solution during the hot-water treatment. This is thought to be because the etching of an aluminum-containing substrate is accelerated, and thus the amount of Al-containing ions in the treatment solution is increased compared to the case of only water.
  • a second method is a method of dispersing AlN in water to prepare a suspension, immersing a substrate in the suspension heated at a predetermined temperature (for example, 70°C), lifting the substrate after a predetermined time has elapsed, and drying the substrate (see Non-Patent Document 1).
  • a predetermined temperature for example, 70°C
  • the method is advantageous in that a fine uneven structure formed of boehmite and bayerite may be formed even on a substrate formed of a material other than the aluminum-containing material.
  • a third method is a method of forming a petal-like structure and a columnar structure separately.
  • any structure may be formed in advance as long as it is possible to form a fine uneven structure.
  • the method is advantageous in that the combination of materials constituting the petal-like structure and materials constituting the columnar structure may be arbitrarily selected.
  • the petal-like structure may be formed on the surface of the columnar structure as well as on the surface of the substrate in some cases.
  • Examples of the method of preparing the petal-like structure include:
  • examples of the method of preparing the columnar structure include:
  • the surface of the fine uneven structure thus-formed is not formed of a metal oxide or a material having a polar functional group (A)
  • the method of introducing the polar functional group (A) is not particularly limited, and a known method may be used.
  • the treatment of introducing a functional group is not always necessary, and a hydroxyl group derived from the chemical structure thereof is already included on the surface thereof.
  • the fine uneven structure when the fine uneven structure is formed of boehmite and bayerite, in order to introduce an amino group into the surface thereof, the fine even structure may be heated while being brought into contact with a gas including an ammonium molecule or may be brought into contact with ammonia plasma.
  • the fine even structure is formed of carbon
  • the fine uneven structure may be irradiated with ultraviolet light while being brought into contact with a gas including an oxygen molecule or steam.
  • the fine uneven structure when the fine uneven structure is formed of carbon, in order to introduce an amino group into the surface thereof, the fine uneven structure may be brought into contact with ammonia plasma.
  • a fourth method is a method of preparing a petal-like structure and a columnar structure simultaneously. For example, a pattern including two regions of a region in which a nickel catalyst is present on a silicon substrate and the other region in which the surface of the silicon substrate is exposed is formed.
  • a pattern including two regions of a region in which a nickel catalyst is present on a silicon substrate and the other region in which the surface of the silicon substrate is exposed is formed.
  • the covering step is a step of covering the surface of the fine uneven structure with a hydrophobic molecule to obtain a hydrophobic molecule-covered unevenness substrate. Details on the hydrophobic molecule are the same as those described above, and thus the description thereof will be omitted.
  • the method of covering the hydrophobic molecule is not particularly limited, and various methods may be used. Typically, the covering with the hydrophobic molecule is performed by dissolving the hydrophobic molecule in a suitable solvent to prepare a solution, coating the solution on the surface of the fine uneven structure, and volatilizing the solvent. By the method, a coating film of the hydrophobic molecule may be formed on the surface of the fine uneven structure. Examples of the coating method of the solution include coating by a brush, dipping, spin coat, sink and the like.
  • the bonding step is a step of forming a chemical bond between the surface of the fine uneven structure and the polar functional group (B) after the covering step, in the case where at least the surface of the fine uneven structure is formed of a metal oxide or a material having a polar functional group (A) and a hydrophobic molecule includes a polar functional group (B) that may form a chemical bond between the molecule and the surface of the fine uneven structure.
  • Super hydrophobicity is exhibited by only physically adsorbing the hydrophobic molecule on the surface of the fine uneven structure. However, durability is low in the case where the hydrophobic molecule is only physically adsorbed.
  • the hydrophobic molecule includes the polar functional group (B) and the surface of the fine uneven structure is in a state capable of being bonded to the polar functional group (B), it is preferred that the surface of the fine uneven structure is covered with the hydrophobic molecule, and then treatment of forming a chemical bond between the fine uneven structure and the polar functional group (B) is performed.
  • the treatment for forming a chemical bond varies depending on the kind of polar functional group (B) or the surface state of the fine uneven structure.
  • the polar functional group (B) is a silanol-based functional group and at least the surface of the fine uneven structure is formed of a metal oxide or a material having a polar functional group (A)
  • the hydrophobic molecule-covered fine uneven substrate may be heated.
  • the heating temperature is preferably 50°C or more.
  • the heating temperature is preferably 300°C or lower.
  • FIG. 1(a) illustrates a schematic cross-sectional view of a hydrophobic material in the related art.
  • FIG. 1(b) illustrates a schematic cross-sectional view of a hydrophobic material according to the present invention.
  • Patent Document 1 when a substrate formed of a metal aluminum foil is subjected to hot-water treatment, a petal-like structure, in which nanosheets formed of boehmite on the surface of the substrate are grown in a vertical direction, is obtained, as illustrated in FIG. 1(a) .
  • a hydrophobic molecule for example, short-chain Rf polymer such as heptadecafluorodecyltrimethoxysilane and the like
  • the surface of the substrate exhibits super hydrophobicity.
  • Water droplets on the surface of the substrate are ideally supported in the vicinity of the vertex of the fine petal-like structure, and the distance from the valley of the petal-like structure to the droplet is short.
  • the surface of the substrate is subjected to predetermined treatment, it is possible to form a fine uneven structure including a fine (for example, a size of nanometer) petal-like structure and a coarse (for example, a size from submicron to micron) columnar structure, as illustrated in FIG. 1(b) .
  • a fine uneven structure including a fine (for example, a size of nanometer) petal-like structure and a coarse (for example, a size from submicron to micron) columnar structure, as illustrated in FIG. 1(b) .
  • the surface of the fine uneven structure is coated with a hydrophobic molecule, the surface of the substrate exhibits super hydrophobicity.
  • the hydrophobic material including the fine uneven structure exhibits excellent super hydrophobicity, compared to a hydrophobic material in the related art including only a petal-like structure.
  • Water droplets on the surface of the substrate are ideally supported in the vicinity of the vertex of the coarse columnar structure, as illustrated in FIG. 1(b) , and thus the distance from the valley of the petal-like structure to the water droplet becomes elongated. That is, water droplets on the surface of the substrate, which are hydrophobic and have a fine uneven structure, are brought into contact with the projections of the fine uneven structure in terms of the microscopic scale, and an air layer is formed between the projections.
  • the smaller the contact area between water droplets and the projections becomes that is, the larger the area of the interface between the air layer formed between the projections and water droplets becomes, the larger the contact angle with water droplets becomes.
  • hydrophobicity is further improved by combining the petal-like structure with the columnar structure is thought to be because the contact area between water droplets and a fine uneven structure is decreased, and the area of the interface between an air layer formed between the projections and droplets is increased.
  • Frost is formed by attaching steam in the atmosphere to the surface of the substrate, then growing the steam into somewhat large water droplets by further introducing other steam in the atmosphere, passing the water droplets through a super-cooling state, and then freezing the water droplets.
  • the super hydrophobic film is applied for preventing frost on the surface of the substrate from being formed, it is necessary to remove water droplets from the surface of the substrate by external wind or water slipping effects before water droplets aggregating on the surface of the substrate are frozen.
  • the surface of the substrate includes a smooth region without the petal-like structure at the lower portion of the columnar structure or between the columnar structures, and is coated with a hydrophobic molecule, super hydrophobicity is not expressed in the smooth region. As a result, it is difficult for water droplets to be removed by external wind or water slipping effects. For this reason, water droplets are grown up to the micrometer scale and then frozen, and thus frost is generated.
  • a combination of the columnar structure and the petal-like structure also has excellent super hydrophobicity against these large water droplets, compared to the structural body formed only of the petal-like structure due to effects of expanding the area of the interface between the air layer/the water droplets by the above-described columnar structure.
  • the hydrophobic material is a composite of the columnar structure and the petal-like structure, and the entire surface thereof is covered with a hydrophobic molecule, the material has excellent super hydrophobicity against water droplets having a size in a wide range from the nanometer scale to the micrometer scale or more.
  • An aluminum substrate is immersed in a polishing solution (concentrated phosphoric acid: 95% by volume, concentrated nitric acid: 5 % by volume, and urea: 30 g/L) heated to about 85°C from 5 minutes to 10 minutes.
  • a polishing solution concentrated phosphoric acid: 95% by volume, concentrated nitric acid: 5 % by volume, and urea: 30 g/L
  • the chemically polished aluminum substrate and a triethylamine aqueous solution (triethylamine: 5% by volume, pure water: 95% by volume) are enclosed in a hermetically sealed container, and then the container is heated at 120°C for three hours.
  • KY-130 (manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in Novec 7200 (manufactured by Sumitomo 3M Limited) to prepare a solution having a polymer concentration: 0.2% by weight. It is described in Japanese Patent Application Laid-Open No. 2009-109612 that the polymer included in KY-130 has a chemical structure represented by Formula (a). Subsequently, the fine uneven substrate manufactured in [1.1.2.] is immersed in the solution for one minute, and then the substrate is lifted from the solution at a pulling rate: 20 cm/min. Thereafter, the sample is subjected to heat treatment at 150°C (Example 1).
  • OPTOOL DSX manufactured by DAIKIN INDUSTRIES, Ltd.
  • OPTOOL DSX is dissolved in perfluorohexane to prepare a solution having a polymer concentration: 0.1% by weight. It is described in Japanese Patent Application Laid-Open No. 2009-109612 that the polymer included in OPTOOL DSX has a chemical structure represented by Formula (b).
  • the fine uneven substrate manufactured in [1.1.2.] is immersed in the solution for one minute, and then the substrate is lifted from the solution at a pulling rate: 20 cm/min. Thereafter, the sample is subjected to heat treatment at 150°C (Example 2).
  • the aluminum substrate is subjected to chemical polishing in the same manner as in Example 1.
  • the aluminum substrate subjected to chemical polishing and pure water are enclosed in a hermetically sealed container, and the container is heated at 120°C for three hours.
  • the surface of the fine uneven substrate manufactured in [1.2.2.] is covered with a hydrophobic molecule represented by Formula (a) in the same manner as in Example 1 (Comparative Example 1).
  • the surface of the fine uneven substrate manufactured in [1.2.2.] is covered with a hydrophobic molecule represented by Formula (b) in the same manner as in Example 2 (Comparative Example 2).
  • FIG. 2 illustrates the relationship between the time and the moving distance during a dynamic sliding test conducted by inclining the surface of a sample after covering with the hydrophobic molecule prepared in Example 2 and Comparative Example 2 by 2° from the horizontal direction.
  • FIG. 3 illustrates the relationship between the time and the moving distance during a dynamic sliding test conducted by inclining the surface of a sample after covering with the hydrophobic molecule prepared in Example 2 and Comparative Example 2 by 1° from the horizontal direction. Even in the measurement at any inclined angle, the acceleration of the water droplet during the sliding is high and the water droplet slides fast in the sample in Example 2, compared to the sample in Comparative Example 2.
  • FIGS. 4 and 5 each illustrate FESEM images of the surface of the samples before and after covering with the hydrophobic molecule prepared in Example 1.
  • FIGS. 6 and 7 each illustrate FESEM images of the surface of the samples before and after covering with the hydrophobic molecule prepared in Comparative Example 1.
  • FIG. 8 illustrates FESEM images observed by inclining the surface of the sample before covering with the hydrophobic molecule prepared in Example 1 by 45°.
  • FIG. 9 illustrates X-ray diffraction patterns of an Al substrate in Example 1 (TEA-added water), an Al substrate in Comparative Example 1 (only water), and an Al substrate (untreated Al) which is subjected to only chemical polishing and is not subjected to fine uneven treatment.
  • a diffraction pattern belonging to boehmite and a diffraction pattern belonging to aluminum of the substrate appear in the sample prepared in Comparative Example 1.
  • a diffraction pattern belonging to bayerite also appears.
  • Example 1 For the fine uneven substrate prepared in Example 1 (without the covering with a hydrophobic molecule), the hydrophobic molecule-covered fine uneven substrates prepared in Example 1 and Example 2 (with the covering with a hydrophobic molecule), and the fine uneven substrate prepared in Comparative Example 1 (without the covering with a hydrophobic molecule), surface analysis is performed by X-ray photoelectron spectroscopy (XPS). The results are shown in Table 1.
  • XPS X-ray photoelectron spectroscopy
  • the concentration of fluorine, silicon and carbon derived from the covered hydrophobic molecule is higher than that of the fine uneven substrate which is not covered with hydrophobic molecules.
  • the thickness of the hydrophobic molecular films is below the XPS detection depth (from several nm to several tens of nm) in that aluminum consisting of a basis is detected.
  • the hydrophobic material and the production process thereof according to the present invention may be used in the body of a vehicle, the hull of a high speed vessel, the external wall of a house, rain gear, clothing, a heat exchanger, an antenna and the like.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Materials For Medical Uses (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
EP12192414.6A 2011-11-14 2012-11-13 Matériau hydrophobe Not-in-force EP2594343B1 (fr)

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JP6206660B2 (ja) * 2013-09-25 2017-10-04 日産自動車株式会社 透明撥水体及びその製造方法
JP6176035B2 (ja) * 2013-09-30 2017-08-09 日産自動車株式会社 微細表面構造体及びその製造方法
JP2016107530A (ja) * 2014-12-08 2016-06-20 株式会社豊田中央研究所 撥水材及びその製造方法
JPWO2018147125A1 (ja) * 2017-02-09 2019-11-07 ダイキン工業株式会社 フィンおよび熱交換器
JP7031790B2 (ja) 2019-04-18 2022-03-08 Dic株式会社 構造体、構造体の製造方法、熱交換機用部材及び熱交換器
JP7373227B2 (ja) * 2019-09-20 2023-11-02 株式会社 山一ハガネ 熱交換器用部材、熱交換器、空気調和機用室内機、空気調和機用室外機、及び冷蔵庫
JP7427240B2 (ja) * 2020-03-30 2024-02-05 学校法人 龍谷大学 表面構造体、およびそれを用いた液滴の回収方法
KR102631226B1 (ko) 2020-04-28 2024-02-01 디아이씨 가부시끼가이샤 발수성 알루미늄재 및 그 제조 방법

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