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WO2010101136A1 - Porous network structure, hydrophilic member utilizing same, and processes for producing the porous network structure and the hydrophilic member - Google Patents

Porous network structure, hydrophilic member utilizing same, and processes for producing the porous network structure and the hydrophilic member Download PDF

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Publication number
WO2010101136A1
WO2010101136A1 PCT/JP2010/053315 JP2010053315W WO2010101136A1 WO 2010101136 A1 WO2010101136 A1 WO 2010101136A1 JP 2010053315 W JP2010053315 W JP 2010053315W WO 2010101136 A1 WO2010101136 A1 WO 2010101136A1
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WIPO (PCT)
Prior art keywords
aluminum
hydrophilic
fine particles
mixed solution
porous structure
Prior art date
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PCT/JP2010/053315
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French (fr)
Japanese (ja)
Inventor
敏明 杉本
多門 坂本
Original Assignee
セントラル硝子株式会社
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Filing date
Publication date
Priority claimed from JP2009048613A external-priority patent/JP2010202924A/en
Priority claimed from JP2009048619A external-priority patent/JP2010202925A/en
Priority claimed from JP2009164920A external-priority patent/JP2011021211A/en
Application filed by セントラル硝子株式会社 filed Critical セントラル硝子株式会社
Publication of WO2010101136A1 publication Critical patent/WO2010101136A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0217—Pretreatment of the substrate before coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0246—Coatings comprising a zeolite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/324—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal matrix material layer comprising a mixture of at least two metals or metal phases or a metal-matrix material with hard embedded particles, e.g. WC-Me
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D15/00—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies
    • F28D15/02—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies in which the medium condenses and evaporates, e.g. heat pipes
    • F28D15/04—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies in which the medium condenses and evaporates, e.g. heat pipes with tubes having a capillary structure
    • F28D15/046—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies in which the medium condenses and evaporates, e.g. heat pipes with tubes having a capillary structure characterised by the material or the construction of the capillary structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • F28F2245/02—Coatings; Surface treatments hydrophilic

Definitions

  • the present invention relates to a mesh-like porous structure formed on the surface of aluminum or an alloy thereof, a hydrophilic member obtained by subjecting the mesh-like porous structure to a hydrophilic treatment, and a method for producing the same.
  • aluminum-based As a method of forming pores by performing surface treatment on aluminum or its alloys (hereinafter collectively referred to as “aluminum-based”), anodization is generally performed on the surface of aluminum or the like using an aqueous solution of sulfuric acid or oxalic acid as an electrolytic bath. So-called “alumite treatment” for forming a film is performed (Patent Document 1). Although this alumite treatment can provide a corrosion-resistant thick film having pores, it has a problem that the process is complicated and that the equipment cost and the power cost are high. Further, in the alumite treatment, although pores of 10 nm to 20 nm are formed, the surface area is not large.
  • a chemical treatment that can form a film only by immersing in a treatment solution, has a relatively simple process and equipment, and has a low treatment cost. Therefore, as such chemical treatment, for example, a so-called “boehmite method” is performed in which a hydrated oxide film is formed on the surface by hot water treatment after immersing aluminum or the like in an amine solution. It is disclosed in Document 2 and the like.
  • the surface treatment by the “boehmite method” is intended to improve corrosion resistance by forming a film on aluminum or its alloy.
  • Patent Document 3 discloses a method of immersing an aluminum material in an aqueous solution of lithium nitrate and caustic soda as a surface treatment method for forming a film by treating an aluminum surface with an alkali hydroxide containing lithium ions.
  • Patent Document 4 discloses a method of treating an aluminum surface with an alkaline solution containing carbon dioxide and carbon dioxide, and a film is formed on the aluminum surface by these methods.
  • the hydrophilic member having the hydrophilic coating layer and the substrate has polarity such as water.
  • it is used as an antifouling article utilizing the affinity, an anti-condensation article, an article with improved polar liquid circulation, and the like.
  • Specific examples of these application fields include members for heat exchange elements such as heat pipes and fins.
  • a film forming process or a coating process is generally performed on the aluminum surface, and the following methods are known.
  • Patent Document 5 A method of forming a hydrophilic film by coating an aluminum surface with a solution containing an alkali silicate (alkali metal silicate), an inorganic curing agent, and a water-soluble organic polymer compound (disclosed in Patent Document 5) (3) A method of imparting hydrophilicity by immersing in an aqueous medium containing a compound having a silanol group and polyvinylpyrrolidone on the surface of a part made of aluminum (disclosed in Patent Document 6) (4) Applying a chromate treatment and then applying an aqueous solution of alkali silicate (alkali metal silicate) containing normal phosphoric acid, then applying a normal phosphoric acid solution, and then heating and drying to form a hydrophilic film Method (disclosed in Patent Document 7)
  • the treatment by the boehmite method is simpler in process and equipment than the alumite treatment, is cheaper in processing cost, and is advantageous in terms of energy saving, but requires a hot water treatment step and takes time to manufacture.
  • the formation of the film is not always regular, and a reticulated porous structure cannot be obtained.
  • Patent Document 3 describes that a hydrated aluminum oxide film can be obtained, but does not describe a mesh-like porous structure.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a network porous structure formed on at least a part of a surface layer portion of aluminum or an alloy thereof by a chemical treatment and a method for producing the same. .
  • the method of the said patent document 5 and the patent document 7 provides hydrophilicity using an alkali silicate (alkali metal silicate), since it has adhered physically to the member. Adhesion is not always sufficient.
  • an alkali silicate strong film is to be formed, it is necessary to treat at a fairly high temperature of 400 ° C., so this is not an industrial technique, and in the case of treatment at a relatively low temperature of about 120 ° C. to 150 ° C. Is not sufficiently cured, and when a hydrophilic coating derived from an alkali silicate is brought into contact with water for a long time, there may be a problem that the hydrophilic portion in the coating gradually disappears.
  • Patent Document 6 has a problem because sufficient hydrophilicity cannot be obtained. Furthermore, the methods described in Patent Document 2, Patent Document 3 and Patent Document 4 describe that a coating of hydrated aluminum oxide is obtained, but it is known that the hydrophilicity of the coating decreases with time. It has been.
  • the present invention aims to solve this problem.
  • the inventors of the present invention have made a series of studies for the purpose of chemically treating an aluminum-based material and forming pores.
  • Surface treatment with a basic mixed solution especially a basic mixed solution having a specific surface tension
  • water and an organic solvent are mixed to improve the wettability with the surface of an aluminum-based material.
  • the inventors have found that a network-like porous structure different from the oxide film is formed on at least a part of the surface layer portion by the rapid reaction between lithium hydroxide and lithium hydroxide.
  • the aluminum-based material is treated with a basic mixed solution (particularly a basic mixed solution having a specific surface tension) in which a base containing lithium hydroxide, water, and an organic solvent are mixed.
  • a basic mixed solution particularly a basic mixed solution having a specific surface tension
  • a base containing lithium hydroxide, water, and an organic solvent are mixed.
  • the inventors have found that a hydrophilic member can be obtained and have reached the present invention.
  • the hydrophilic composite member obtained by further subjecting the hydrophilic member to hydrophilic treatment maintains good hydrophilicity.
  • a reticulated porous structure is formed by treating an aluminum material with a solution or suspension obtained by mixing “hydrophilic fine particles” with “basic mixed solution containing lithium hydroxide”. It was found that a hydrophilic member excellent in adhesiveness in which hydrophilic fine particles are rapidly supported from the side to be supported and hydrophilic fine particles are more firmly supported by a simple process can be obtained.
  • hydrophilic fine particles such as colloidal metal oxides and phyllosilicates react with alkali metal hydroxides, and there is a possibility of forming different forms of salts depending on the reaction.
  • Mixing and suspending hydrophilic fine particles in a basic mixed solution containing lithium hydroxide is a process that is not normally performed.
  • the inventors have made the aluminum-based material a base containing lithium hydroxide and water.
  • a basic mixed solution especially a basic mixed solution having a specific surface tension
  • an organic solvent By treating with a basic mixed solution (especially a basic mixed solution having a specific surface tension) mixed with an organic solvent, the wettability with the surface of the aluminum-based material is improved.
  • a network-like porous structure different from the oxide film was formed on at least a part of the surface layer portion, and the present invention was reached.
  • an aluminum-based functional member can be easily produced by supporting and fixing functional fine particles using the network porous structure as a carrier.
  • the base material is made of aluminum or an alloy thereof, and at least a part of the surface layer is formed by treating with a basic mixed solution in which a base containing lithium hydroxide, water, and an organic solvent are mixed.
  • a mesh-like porous structure characterized in that the mesh-like porous structure comprises pores having a pore diameter of 5 nm to 500 nm and a depth of 0.0 ⁇ m to 5 ⁇ m,
  • the network porous structure is useful as a carrier for fine particles, and a functional member can be produced by supporting and fixing fine particles having functionality.
  • the present invention includes the following inventions 1 to 5.
  • invention 1 A network-like porous structure formed by contact treatment of at least part of the surface layer portion with a basic mixed solution in which a base containing lithium hydroxide, water and an organic solvent are mixed, the base material being made of aluminum or an alloy thereof.
  • a reticulated porous structure wherein the reticulated porous structure includes pores having a pore diameter of 5 nm to 500 nm and a depth of 0.05 ⁇ m to 10 ⁇ m.
  • invention 2 By subjecting aluminum or an alloy thereof to a contact treatment with a basic mixed solution in which a base containing lithium hydroxide, water, and an organic solvent are mixed, at least a part of the surface layer portion of aluminum or the alloy has a mesh-like porous structure.
  • invention 3 3. The method for producing an aluminum-based hydrophilic member according to invention 2, wherein the mixed solvent constituting the basic mixed solution has a surface tension in the range of 18 mN / m to 60 mN / m.
  • the organic solvent in the basic mixed solution is at least one of an alcohol, nitrile, ketone, ester, ether, sulfoxide, amide, glycol, aromatic, or fluorinated alcohol solvent.
  • Invention 5" The method for producing a reticulated porous structure according to any one of Inventions 2 to 4, wherein the pH of the basic mixed solution is in the range of 9.0 to 13.5.
  • the present inventors performed various chemical treatments on the aluminum-based material to form pores, thereby improving the hydrophilicity in the course of a series of studies,
  • a basic mixed solution particularly a basic mixed solution having a specific surface tension
  • a base containing lithium oxide, water, and an organic solvent are mixed
  • the wettability with the surface of the aluminum-based material is improved.
  • a rapid reaction between the surface and lithium hydroxide proceeds, and a network-like porous structure different from the oxide film is formed on at least a part of the surface layer portion, thereby obtaining a hydrophilic member with significantly improved hydrophilicity.
  • the present invention has been reached.
  • the hydrophilic composite member obtained by further subjecting the hydrophilic member to hydrophilic treatment maintains good hydrophilicity.
  • the aluminum-based hydrophilic member is obtained by treating the aluminum-based material with a basic mixed solution obtained by mixing a base containing at least lithium hydroxide, water, and an organic solvent, thereby at least one surface of the aluminum-based material.
  • a mesh-like porous structure is formed on the part (first step).
  • the present invention includes the following invention 6 to invention 14.
  • invention 6 A network-like porous structure formed by contact treatment of at least part of the surface layer portion with a basic mixed solution in which a base containing lithium hydroxide, water and an organic solvent are mixed, the base material being made of aluminum or an alloy thereof.
  • An aluminum-based hydrophilic member characterized in that the network porous structure includes pores having a pore diameter of 5 nm to 500 nm and a depth of 0.05 ⁇ m to 10 ⁇ m. .
  • invention 7 The manufacturing method of the aluminum-type hydrophilic member which consists of the following and 1st processes.
  • invention 8 8. The method for producing an aluminum-based hydrophilic member according to invention 7, wherein the surface tension of the mixed solvent constituting the basic mixed solution is in the range of 18 mN / m to 60 mN / m.
  • the organic solvent in the basic mixed solution is at least one of an alcohol, nitrile, ketone, ester, ether, sulfoxide, amide, glycol, aromatic, or fluorinated alcohol solvent.
  • invention 10 The method for producing an aluminum-based hydrophilic member according to any one of Inventions 7 to 9, wherein the pH of the basic mixed solution is in the range of 9.0 to 13.5.
  • invention 11 Invention 7 thru
  • the manufacturing method of the aluminum type composite hydrophilic member as described in any one.
  • “Invention 12” Hydrophilic fine particles are colloidal silica, colloidal alumina, colloidal titania, zeolite, silica gel, silica, alumina, titania, calcium carbonate, calcium oxide, talc, diatomaceous earth, vermiculite, vermiculite, petal, shell calcined calcium fine particles, Alternatively, the aluminum according to invention 11, which is at least one selected from the group consisting of nanometal particles or nanometal colloids of gold, silver, platinum, palladium, ruthenium, copper, nickel, vanadium, titanium, indium, tin, and tungsten. Of producing a composite composite hydrophilic member.
  • invention 13 The aluminum-based composite hydrophilic member according to invention 11 or invention 12, wherein in the second step, the hydrophilic fine particles are supported so that the mass of the hydrophilic fine particles is within a range of 0.1 g / m 2 to 20 g / m 2. Manufacturing method.
  • invention 14 An aluminum-based composite hydrophilic member produced by the production method according to any one of Inventions 11 to 13.
  • the present inventors conducted extensive studies to solve the above problems, and found that a solution or suspension obtained by mixing “hydrophilic fine particles” with “basic mixed solution containing lithium hydroxide” was obtained.
  • hydrophilic fine particles are quickly supported from the side on which the network porous structure is formed, and the hydrophilic fine particles are more firmly supported by a simple process.
  • the present inventors have found that an excellent hydrophilic member can be obtained and have reached the present invention.
  • hydrophilic fine particles such as colloidal metal oxides and phyllosilicates react with alkali metal hydroxides, and there is a possibility of forming different forms of salts depending on the reaction.
  • Mixing and suspending hydrophilic fine particles in a basic mixed solution containing lithium hydroxide is a process that is not normally performed.
  • aluminum or an alloy thereof is contact-treated with a solution or suspension obtained by mixing hydrophilic fine particles in a basic mixed solution obtained by mixing a base containing lithium hydroxide, water, and an organic solvent.
  • a solution or suspension obtained by mixing hydrophilic fine particles in a basic mixed solution obtained by mixing a base containing lithium hydroxide, water, and an organic solvent can be produced.
  • the present invention includes the following inventions 15 to 21.
  • invention 15 By subjecting aluminum or an alloy thereof to contact treatment with a solution or suspension obtained by mixing hydrophilic fine particles in a basic mixed solution obtained by mixing a base containing lithium hydroxide, water and an organic solvent, aluminum or an alloy thereof is obtained.
  • An aluminum-based hydrophilic member characterized in that a network-like porous structure is formed on at least a part of the surface layer portion, and the hydrophilic fine particles are supported and fixed on the network-like porous structure.
  • invention 16 16.
  • the organic solvent in the basic mixed solution is at least one of an alcohol, nitrile, ketone, ester, ether, sulfoxide, amide, glycol, aromatic, or fluorinated alcohol solvent.
  • invention 18 The aluminum-based hydrophilic member according to any one of Inventions 15 to 17, wherein the pH of the basic mixed solution is in the range of 9.0 to 13.5.
  • invention 19 The aluminum-based hydrophilic member according to invention 15, wherein the network porous structure includes pores having a pore diameter of 5 nm to 500 nm and a depth of 0.05 ⁇ m to 10 ⁇ m.
  • Hydrophilic fine particles are colloidal silica, colloidal alumina, colloidal titanium, colloidal tin, colloidal antimony, colloidal mullite, colloidal iron, alumina, zeolite, silica gel, silica, alumina, titania, calcium carbonate, calcium oxide, talc, diatomaceous earth, vermiculite, leech Selected from the group consisting of fine particles of stone, petals, shell calcined calcium, or nanometal particles or colloidal metal of gold, silver, platinum, palladium, ruthenium, copper, nickel, vanadium, titanium, indium, tin, tungsten
  • the aluminum-based hydrophilic member according to invention 15 which is at least one.
  • invention 21 The aluminum-based hydrophilic member according to invention 15, wherein the hydrophilic fine particles are supported so that the mass of the hydrophilic fine particles is within a range of 0.1 g / m 2 to 20 g / m 2 .
  • Example 2 is a SEM photograph of an aluminum plate having a network porous structure obtained in Example 1.
  • 4 is a SEM photograph of an aluminum nonwoven fabric having a network porous structure obtained in Example 4.
  • 6 is an SEM photograph of an aluminum nonwoven fabric in which zeolite particles are supported on a mesh-like porous material obtained in Example 5.
  • 4 is an SEM photograph of an aluminum plate contact-treated with a (sodium hydroxide / water / ethanol) mixed solution obtained in Comparative Example 2.
  • FIG. (No reticulated microporous structure was observed.) 4 is an SEM photograph of an aluminum plate in which IPA-ST fine particles are supported on a mesh-like porous material obtained in Example 10.
  • 6 is a SEM photograph of an aluminum plate having kaolinite fine particles supported on a mesh-like porous material obtained in Example 15.
  • the porous porous body of the present invention is useful as a carrier, fine particles having catalyst, dye, adsorptive, hydrophilic, and water-repellent functionalities are supported and fixed in the porous body. Therefore, it is useful as a functional material having this function.
  • the network porous body can be easily produced by a simple method of treating an aluminum-based material with a mixed base solution in which a base containing lithium hydroxide, water and an organic solvent are mixed.
  • the aluminum-based hydrophilic member of the present invention is industrially useful because a member in which hydrophilic particles are supported on a mesh-like porous structure can be obtained by a relatively simple method.
  • hydrophilic fine particles are rapidly supported from the side on which the mesh-like porous structure is formed, so that a hydrophilic member that is easy to manufacture and has excellent adhesion can be obtained. It is done.
  • the hydrophilic member is useful as a member of a heat exchange element such as a heat pipe or a fin because it exhibits super hydrophilicity.
  • the present invention is as follows.
  • the inventors of the present invention have made a series of studies for the purpose of chemically treating an aluminum-based material and forming pores.
  • Contact treatment with a basic mixed solution especially a basic mixed solution having a specific surface tension
  • water and an organic solvent are mixed to improve the wettability with the surface of the aluminum-based material.
  • a network-like porous structure different from the oxide film is formed on at least a part of the surface layer portion by the rapid reaction between lithium hydroxide and lithium hydroxide.
  • the network-like porous structure of the present invention targets an aluminum-based material, and has network-like microporous pores formed on at least a part of its surface.
  • the aluminum-based material that is the subject of the present invention is pure aluminum having a purity of 99.9% by mass or more and various aluminum alloys.
  • Specific examples of the aluminum alloy include alloys containing trace amounts of Si, Fe, Cu, Mn, Mg, etc., such as A1050, A1070, A1080, A1100, A1200, etc., and particularly, A2014, A2017, A2024, etc.
  • alloys particularly rich in Zn such as A7075, A7N01, etc.
  • casting alloys containing a large amount of Si such as ADC12, etc.
  • aluminum-based material aluminum foil, ingot, plate, pipe, aluminum fiber, die cast, intermediate products made of these aluminums, and finished products made of aluminum are all included in the category of aluminum of the present invention.
  • the aluminum-based network porous structure of the present invention is obtained by subjecting an aluminum-based material to contact treatment with a basic mixed solution obtained by mixing a base containing lithium hydroxide, water, and an organic solvent, and at least a part of the surface of the aluminum-based material. Can be produced by forming a mesh-like porous structure.
  • the “solution” in the present invention means that the solute is completely dissolved in the solvent, and does not include those in which the solute is dispersed or suspended in the solvent.
  • a mixed solvent shall be uniform, without isolate
  • a base such as lithium hydroxide is completely dissolved in the solute.
  • the solvent in the basic mixed solution is a mixed solvent of water and an organic solvent, and a hydrophilic solvent described later is usually used as the organic solvent.
  • the surface tension of the mixed solvent By adjusting the surface tension of the mixed solvent, the wettability with the surface of the aluminum-based material is improved as will be described later, so that the reaction between the aluminum surface and lithium hydroxide proceeds promptly.
  • Such surface tension is in the range of 18 mN / m to 60 mN / m, preferably 20 mN / m to 55 mN / m, and more preferably 20 mN / m to 50 mN / m.
  • the surface tension of water is about 72 mN / m at 20 ° C., but the surface tension can be reduced by adding an organic solvent.
  • the wettability to the aluminum surface is excellent, but the water content becomes extremely small and lithium hydroxide does not dissolve, which is not preferable. Moreover, when surface tension becomes larger than 50 mN / m, since the wettability to the aluminum surface worsens, it is not preferable.
  • the mixing ratio of the organic solvent and water Is preferably an organic solvent / water ratio of 90/10 to 10/90, and particularly preferably 70/30 to 30/70.
  • the preparation method is Although it does not specifically limit, Usually, after preparing the solution containing lithium hydroxide, the method of adding and preparing an organic solvent is used. As in the case of the basic mixed solution, the basic solution containing lithium hydroxide needs to dissolve a solute such as lithium hydroxide, and the solvent is “water alone” or “water and a hydrophilic organic solvent. It is preferable to use a “mixed solvent”.
  • “1” A method for preparing a basic solution by dissolving a solute such as lithium hydroxide in water, and then adding a hydrophilic organic solvent.
  • “2” A solute such as lithium hydroxide containing “water and hydrophilic organic”. Examples of the method include adding a solvent mixed solvent and dissolving it to prepare a basic solution, and then adding the same or another organic solvent, but the method of “1” is usually preferably used.
  • hydrophilic solvent alcohol-based, nitrile-based, ketone-based, ether-based, sulfoxide, amide-based, ester-based and glycol-based solvents having 1 to 7 carbon atoms are preferably used.
  • the solvent examples include methanol, ethanol, isopropanol, acetonitrile, propyronitrile, acetone, methyl ethyl ketone, dimethyl ketone, methyl isobutyl ketone, dimethyl ether, diethyl ether, dioxane, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, dimethyl sulfoxide, dimethyl
  • examples include, but are not limited to, formamide, dimethylacetamide, methyl formate, ethyl formate, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, ethylene glycol, propylene glycol and the like.
  • methanol and ethanol are particularly preferable because of availability.
  • these solvents can be used 1 type or in mixture of 2 or more types.
  • an organic solvent is further mixed with the basic solution to prepare a basic mixed solution.
  • a solute such as lithium hydroxide does not precipitate due to the mixing of the basic solution and the organic solvent.
  • the hydrophilic solvent is preferably used as the organic solvent to be used.
  • the solvent of the basic solution is “a mixed solvent of water and a hydrophilic organic solvent”
  • the same kind or another hydrophilic organic solvent is further added as an organic solvent from the above hydrophilic organic solvents.
  • an aromatic solvent or a fluorinated alcohol solvent can be used for the purpose of further improving wettability to the surface of the aluminum material.
  • solvents include, but are not limited to, benzene, toluene, xylene, hexafluoroisopropyl alcohol, and the like.
  • these solvents can be used 1 type or in mixture of 2 or more types.
  • the pH of the basic mixed solution is desirably in the range of pH 9.0 to pH 13.5. If the pH is less than 9.0, the reaction does not proceed. If the pH exceeds 13.5, the coating is eroded violently or the network porous structure is destroyed, which is not preferable.
  • the concentration of the solute that gives such pH depends on the difference in the solubility of the base such as lithium hydroxide in the mixed solvent constituting the basic mixed solution, and thus cannot be specified unconditionally. Is preferably 5% by mass, and more preferably 1.0% by mass to 3.5% by mass. If the amount is less than 0.5% by mass, the reaction is insufficient. On the other hand, if the amount exceeds 5% by mass, the coating is vigorously eroded or the network porous structure is destroyed, which is not preferable.
  • the mixed solution is an aqueous solution containing no organic solvent (surface tension: about 72 mN / m)
  • the surface of the aluminum-based material is water-repellent, so that the wettability is deteriorated.
  • the basic solution is repelled. Therefore, a uniform reaction is difficult to proceed, which is not preferable.
  • a basic aqueous solution there exists a fault that reaction with an aluminum-type material does not advance easily, and several tens of induction time is required until reaction advances. This is probably because an aluminum oxide film of several nm existing on the surface of aluminum works as a passive state.
  • the wettability with the aluminum surface is improved by adjusting the surface tension of the mixed solution within the range of 18 mN / m to 60 mN / m using an organic solvent. It is possible to react uniformly regardless of unevenness. Furthermore, since the reaction proceeds promptly, an aluminum-based hydrophilic member in which a uniform network porous structure is formed on the surface of the aluminum material can be produced in 30 seconds to 10 minutes.
  • degreasing and surface activation treatment of the aluminum material may be performed before the treatment in the first step, but this is not an industrial method because the operation becomes complicated. Since the basic mixed solution containing lithium hydroxide has a certain degree of degreasing power, the production method of the present invention is an excellent method that can omit degreasing and surface activation treatment.
  • an alkali metal hydroxide or an alkaline earth metal hydroxide is further added as a solute in addition to lithium hydroxide.
  • Examples of the alkali metal hydroxide used include hydroxides such as sodium hydroxide, lithium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.
  • Examples of the alkaline earth metal hydroxide include hydroxides such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide.
  • alkali metal hydroxides and alkaline earth metal hydroxides differ in solubility in solvents and base strength, they cannot be specified unconditionally.
  • the solute contained in the mixed solution is “lithium hydroxide and others.
  • the concentration of “alkaline metal hydroxide” or “lithium hydroxide and alkaline earth metal hydroxide” includes a minimum of 0.5% by mass of lithium hydroxide and a total of “greater than 0.5% by mass and 5% by mass. % Or less "is desirable.
  • the pH range is adjusted to 9.0 by appropriately adjusting the mixing ratio of “lithium hydroxide and other alkali metal hydroxide” or “lithium hydroxide and alkaline earth metal hydroxide”. To 13.5.
  • the concentration of the basic mixed solution is preferably 1.0% by mass to 3.5% by mass.
  • the aluminum-based material when an aluminum-based material is treated with a basic mixed solution, the aluminum-based material needs to be brought into contact with the basic mixed solution.
  • the method of contacting is not particularly limited, and examples thereof include a method of spraying the basic mixed solution with a spray, a method of dropping with a syringe or the like, and a method of immersing in a processing bath of the basic mixed solution.
  • a dipping method is preferably used.
  • the immersion time in the treatment bath may be selected appropriately depending on the type, shape, and dimensions of the aluminum-based material, the concentration of the basic aqueous solution, the composition, the bath temperature, etc., and is usually set to 30 seconds to 15 minutes. Is done.
  • the bath temperature may be set to an appropriate temperature in consideration of the immersion time.
  • the basic solution is set to room temperature to about 50 ° C., more preferably 20 ° C. to 40 ° C. Set to ° C.
  • the temperature is lower than the above temperature range, the time required for the reaction to proceed is very long.
  • the temperature is high, the reaction becomes too fast, the coating is eroded violently, the mesh porous structure is destroyed, the surface Tends to be non-uniform.
  • the drying treatment may be performed at normal temperature or may be heated and dried with hot air. It is also possible to heat the aluminum substrate to a certain temperature (about 100 ° C. to 350 ° C.) after drying, and various methods are performed without any particular limitation.
  • a certain temperature about 100 ° C. to 350 ° C.
  • the solvent mixture of hydrophilic organic solvent and water gradually evaporates from the surface, and in the process, alkali components remain on the surface and the concentration gradually increases and reacts from the aluminum surface.
  • a network structure is formed in which the crystal grains of metal crystals are eluted and leave the grain boundary walls.
  • the drying process is not essential, the above-described drying process may be performed for the purpose of forming a sufficient network structure. desirable.
  • the network porous structure is useful as a carrier, and supports and immobilizes fine particles having functions such as catalyst, dye, adsorptivity, hydrophilicity, and water repellency in the porous structure. It is possible to express functionality.
  • the particle diameter of the fine particles is not particularly limited, but is preferably in the range of 5 nm to 50 ⁇ m. If the average particle size is less than 5 nm, the particle size of the fine particles is too small, requiring a long coating time, resulting in poor efficiency. Also, the surface energy of the fine particles becomes very large, making monodispersion difficult and easy to aggregate. Is very difficult. On the other hand, if the average particle size of the fine particles exceeds 50 ⁇ m, the influence of gravity increases because the particle size is much larger than the pore size of the mesh-like porous structure on the coating, and the fine particles incorporated in the pore size cannot be retained. The problem of peeling off easily due to friction occurs. More preferably, it is 0.05 ⁇ m to 40 ⁇ m, and still more preferably 0.5 ⁇ m to 20 ⁇ m.
  • the particle size of the particles referred to here indicates the size of so-called primary particles, and does not indicate the size of secondary particles in which fine particles are aggregated.
  • the size of the secondary particles is not particularly limited as long as there is no difficulty in film formation.
  • a fine particle suspension is prepared.
  • the solvent is not particularly limited as long as it can prepare a suspension of fine particles, but may be appropriately selected in consideration of wettability of the selected fine particles. Specifically, water, methanol, ethanol, i-propanol, n-propanol, n-butanol, i-butanol, t-butanol, alcohols such as methoxyethanol, ethoxyethanol, ethylene glycol, acetate ester, carboxylic acid, A suspension in which the fine particles are suspended is prepared using a solvent composed of a general solvent such as lower hydrocarbon, aliphatic, aromatic, or a mixture thereof. Moreover, you may add a dispersing agent etc. in order to improve a dispersibility.
  • the method for supporting and immobilizing the fine particles on the network porous structure is not particularly limited as long as the fine particles can be introduced, and a method of coating the suspension or a method of impregnating the suspension may be used. Can be mentioned.
  • wet coating can be performed by means of dip coating, flow coating, spray coating, plating, electroless plating, screen printing, flexographic printing, etc., and dip coating, spray coating, plating, no Electroplating is suitably used as a simple method.
  • Suspension coating can also be carried out dry, by applying a method in which the powder charged by the electrostatic coating method is made to collide with the oppositely charged sample for efficient adhesion, or the hydrophilic fine particles are applied at high speed by the blast method.
  • a method of spraying and finely coating the fine holes is preferably used.
  • Methods for impregnating the suspension include atmospheric pressure impregnation method, reduced pressure impregnation method, pressure impregnation method, sol-gel method, electrophoresis method, immersion ultrasonic impregnation method, etc.
  • a pressure impregnation method and an immersion ultrasonic parent method are preferably used.
  • the impregnation method using pressure reduction and pressurization is preferable.
  • an aluminum member having a network-like porous structure is placed in a suitable vacuum vessel, the pressure inside is reduced, and the suspension of the fine particles is introduced into the surface pores.
  • the fine particles can be densely packed. It is also possible to fill the container with more fine particles by introducing the suspension and then pressurizing the container.
  • the immersion ultrasonic method is also preferably used, and the fine particles are introduced while immersing the aluminum member in which the mesh-like porous structure is formed in the suspension and applying ultrasonic waves. Can be filled with fine particles.
  • the film After introducing the fine particles by coating or impregnation, the film can be formed by drying and heating, and the fine particles can be supported and fixed.
  • the drying / heating treatment method is not particularly limited, and may be dried at room temperature or may be heated and dried with hot air. Further, after drying, a method in which the aluminum base material is further heated to 100 ° C. to 350 ° C. and further dried is used. For example, after drying at room temperature for 30 minutes, a method of heating in an oven at 150 ° C. for about 1 hour is used. In this way, an aluminum based composite hydrophilic member can be produced.
  • fine particles having the functionality for example, fine particles having an adsorptive property can be supported, and when adsorbing function is carried out by using a zeolite having a particle size of about 10 nm to 500 nm (for example, zeolite) filled and supported. It can be set as the aluminum member which provided.
  • a zeolite having a particle size of about 10 nm to 500 nm for example, zeolite
  • a photocatalyst As fine particles having a catalytic function, for example, a photocatalyst can be supported, and when filled and supported using titanium oxide (for example, trade name, ST series, manufactured by Ishihara Sangyo Co., Ltd.), aluminum provided with a photocatalytic function It can be a member.
  • titanium oxide for example, trade name, ST series, manufactured by Ishihara Sangyo Co., Ltd.
  • aluminum provided with a photocatalytic function It can be a member.
  • metal having an oxidation catalyst ability when introduced, it becomes possible to decompose harmful gases, volatile organic compounds, etc., and to make a member having an environmental purification function.
  • metals include palladium, platinum, ruthenium, rhodium, iridium, nickel, cobalt, manganese, and the like, and an impregnation method using a solution of the metal salt is preferably used.
  • an aluminum member having a network porous structure according to the present invention is immersed in an aqueous solution of chloroplatinic acid to fill the network porous membrane with chloroplatinic acid crystals, and then in the air. Filling and supporting / immobilizing can be performed by reducing platinum oxide particles after firing.
  • the network porous structure of the present invention is useful as a carrier for supporting fine particles, and a functional aluminum member can be easily produced by supporting fine particles having functionality.
  • the aluminum-based material is treated with a basic mixed solution (particularly a basic mixed solution having a specific surface tension) in which a base containing lithium hydroxide, water, and an organic solvent are mixed.
  • a basic mixed solution particularly a basic mixed solution having a specific surface tension
  • a base containing lithium hydroxide, water, and an organic solvent are mixed.
  • the inventors have found that a hydrophilic member can be obtained and have reached the present invention.
  • the hydrophilic composite member obtained by further subjecting the hydrophilic member to hydrophilic treatment maintains good hydrophilicity.
  • a hydrophilic member made of a network-like porous structure formed on the surface of aluminum or an alloy thereof (hereinafter sometimes referred to as an aluminum group), and a composite hydrophilic property obtained by subjecting the hydrophilic member to further hydrophilic treatment The members and the manufacturing method thereof will be described.
  • An aluminum-based hydrophilic member treats an aluminum-based material as a base material with a basic mixed solution in which a base containing lithium hydroxide, water, and an organic solvent are mixed, and at least part of the surface of the aluminum-based material has a mesh shape. It can be produced by the above-mentioned network-like porous structure for forming the porous structure and the production method (first step). Although the hydrophilic member itself exhibits excellent hydrophilicity, further hydrophilic treatment (second step) using the network-like microporous structure of the aluminum-based hydrophilic member obtained in the first step as a carrier. ), An aluminum based composite hydrophilic member having functionality can be manufactured.
  • the aforementioned aluminum materials are preferably used.
  • the mesh-shaped material has a large surface area, and thus is suitably used for applications such as fins for heat exchange elements, hydrophilic films for low-temperature humidifiers, and the like.
  • the mesh-like aluminum-based material can be obtained as an aluminum metal nonwoven fabric.
  • the aluminum metal nonwoven fabric sheet is formed by rolling a sintered aluminum metal cotton sheet obtained by depositing aluminum metal fibers in a plate shape, and is complicatedly folded between the aluminum fibers. There is a feature that is large.
  • the first step is the same as the above-described network-like porous structure and its manufacturing method.
  • the aluminum-based hydrophilic member of the present invention can be produced from the following first step.
  • First step By treating aluminum or an alloy thereof with a basic mixed solution in which a base containing at least lithium hydroxide, water, and an organic solvent are mixed, at least a part of the surface layer portion of aluminum or the alloy is formed into a mesh. Forming a fine porous pore.
  • the pores having a pore diameter of 5 nm to 500 nm and a depth of 0.05 ⁇ m to 10 ⁇ m were reticulated. It was observed that they were regularly arranged, and it was found to have a reticulated porous structure.
  • the pure water contact angle is desirably 30 degrees or less. This is because if the pure water contact angle exceeds 30 degrees, the predetermined hydrophilicity cannot be obtained. More preferably, it is 20 degrees or less, and more preferably 10 degrees or less.
  • the pure water contact angle is set to 30 degrees or less. For example, if the pure water contact angle is smaller than 5 degrees, high-precision measurement becomes difficult, but the hydrophilicity of the pure water contact angle is extremely close to 0 degrees. It is because the case where it shows is also included. In this specification, when a pure contact angle of 10 degrees or less is shown, it is evaluated as “superhydrophilic”. The pure water contact angle is measured according to JIS R 3257: 1999 “Test method for wettability of substrate glass surface”.
  • the pure water contact angle of the aluminum-based member having the network porous structure obtained in the first step is measured, the water droplet spreads on the surface of the coating and becomes so small that the contact angle cannot be measured, and the coating is super hydrophilic. Can be observed.
  • the second step produces a functional aluminum-based composite hydrophilic member by performing further hydrophilic treatment using the mesh-like microporous structure of the aluminum-based hydrophilic member obtained in the first step as a carrier. It is a process to do.
  • hydrophilic treatment hydrophilicity is imparted to the surface, and the apparent pure water contact angle becomes more hydrophilic, making it difficult for initial fine water droplets to adhere and grow, and to express super hydrophilicity.
  • a hydrophilic coating is obtained.
  • the hydrophilic treatment in the second step of the present invention is to carry and fix hydrophilic functional fine particles with the porous portion of the aluminum-based member having a network porous structure obtained in the first step as a carrier. Objective. This step makes it possible to produce an aluminum-based composite hydrophilic member.
  • the aluminum-based hydrophilic member obtained in the first step is a network-like porous structure having a hydrophilic pore diameter of 5 nm to 500 nm.
  • hydrophilic fine particles that fit the pore size of the porous structure as anchors By introducing hydrophilic fine particles that fit the pore size of the porous structure as anchors, the fine particles that are both hydrophilic and the porous structure adhere to each other, thereby having strong adhesion.
  • Some of the inorganic fine particles used have a particle diameter larger than 500 nm, but a strong bond is formed between the outermost surface portion of the inorganic fine particles that have entered the hole as an anchor and the larger inorganic fine particles. Therefore, it is considered that the fine particles in the pores hold the particles outside the membrane, form a complex surface, and are covered with a coating having a large specific surface area. Since the coating is composed of hydrophilic fine particles, it exhibits excellent hydrophilicity and is useful as an aluminum-based hydrophilic composite member.
  • the particle diameter of the fine particles is not particularly limited, but is preferably in the range of 5 nm to 50 ⁇ m. If the average particle size is less than 5 nm, the particle size of the fine particles is too small, requiring a long coating time, resulting in poor efficiency. Also, the surface energy of the fine particles becomes very large, making monodispersion difficult and easy to aggregate. Is very difficult. On the other hand, if the average particle size of the fine particles exceeds 50 ⁇ m, the influence of gravity increases because the particle size is much larger than the pore size of the mesh-like porous structure on the coating, and the fine particles incorporated in the pore size cannot be retained. The problem of peeling off easily due to friction occurs. More preferably, it is 0.05 ⁇ m to 40 ⁇ m, and still more preferably 0.5 ⁇ m to 20 ⁇ m.
  • the particle size of the particles referred to here indicates the size of so-called primary particles, and does not indicate the size of secondary particles in which fine particles are aggregated.
  • the size of the secondary particles is not particularly limited as long as there is no difficulty in film formation.
  • the mass per unit area of the supported hydrophilic fine particles needs to be within the range of 0.1 g / m 2 to 20 g / m 2 . If the mass per unit area of the hydrophilic fine particles is less than 0.1 g / m 2 , it is not preferable because sufficient coating is not performed and unevenness occurs in the coating. On the other hand, when the mass of the hydrophilic fine particles exceeds 20 g / m 2 , the mesh-like porous material is covered with the fine powder over the entire surface, and the mesh-like porous material is completely buried to reduce the surface area, resulting in poor hydrophilicity. Not only is it economical, but it can be easily peeled off by friction and vibration, causing a significant hindrance to mechanical strength.
  • hydrophilic fine particles used include colloidal silica, colloidal alumina, colloidal titania, zeolite, silica gel, silica, alumina, titania, calcium carbonate, calcium oxide, talc, diatomaceous earth, vermiculite, leechite, petal, shell fired Calcium and phyllosilicates, metal fine particles, etc. are raised, and at least one selected from these groups is preferably used.
  • diatomaceous earth, zeolite, silica gel, shell calcined calcium and phyllosilicate can exhibit water absorption, antibacterial properties and the like due to their porous properties, and increase the added value of the article of the present invention.
  • calcined shell calcium and phyllosilicates can be used, and the use of calcined shell calcium and phyllosilicates is particularly preferred.
  • These fine particles can be used in combination.
  • mica which is a phyllosilicate
  • silver particles of metal fine particles can be mixed to form a suspension.
  • the shell calcium calcined Since the shell calcium calcined has a large specific surface area, it has the effect of increasing the water surface adsorption and maintaining the hydrophilicity for a long time. In addition to its own calcium source, it is also used as a source of calcium, as a pesticide for pathogens, bacteria, etc., for cleaning residual agricultural chemicals in vegetables and fruit trees, and as a pharmaceutical product. The effect can be expected. Accordingly, when shell calcined calcium is introduced as fine particles, it is possible to add not only the maintenance of hydrophilicity but also an antibacterial function.
  • Calcium shell calcium is calcium oxide (CaO) or calcium oxide and carbonic acid obtained by gradually decarboxylation (removing carbon dioxide) by firing shells whose main component is calcium carbonate before firing. It is a mixture of calcium.
  • firing 99% by mass of calcium carbonate, which is the main component before firing, is gradually converted into calcium oxide, and at the same time, firing of 1% by mass of organic matter contained in the shell before firing also proceeds simultaneously.
  • the firing temperature when the firing temperature is increased, all of the calcium carbonate is converted to calcium oxide, but when the firing temperature is low, part of the calcium carbonate is changed to calcium oxide, but the rest remains as calcium carbonate.
  • the component of the calcined shell shell calcium to be used is not particularly limited as long as a part of the calcium carbonate can be converted to calcium oxide.
  • calcium carbonate as the main component of the shell and the calcined product thereof. It is preferable to use calcium oxide obtained by doing this, a mixture of calcium oxide and calcium carbonate, or a mixed state thereof (mixed calcium oxide and calcium carbonate).
  • the proportions of calcium carbonate and calcium oxide and each component differ depending on the firing temperature and firing time, and can be adjusted as appropriate.
  • the calcination temperature when producing shell-calcined calcium is usually 500 ° C. to 1200 ° C. Preferably, it is in the temperature range of 600 ° C to 1100 ° C.
  • the firing time varies depending on the firing temperature, but can be appropriately adjusted in order to obtain the above-mentioned shell-fired calcium in a preferred ratio.
  • the shell used as the shell-calcined calcium is preferably a hydrophilic coating in which at least one kind is selected from scallops, abalone, oysters, and oysters.
  • the shell used in the present invention is not particularly limited as long as the component before baking contains calcium carbonate as a main component, and specifically, red shellfish, clams, scallops, abalone, oysters, basilis. (Sea bream), mussels, cherry mussels, turban shells, rainbow trout, snails, snails, tiger oysters, clams, snails, etc. are used.
  • particularly preferred are scallop, abalone, oyster, and crabs shells.
  • the phyllosilicate is characterized in that metal ions such as aluminum, sodium, calcium, magnesium, etc. and silicic acid are linked to form a tetrahedral sheet layered structure. It is known that the interstices of the tetrahedral sheet layer structure have a property of exchanging metal ion organic substances and the like, and have a property of taking in water, and therefore exhibit extremely good hygroscopicity. Furthermore, improvement in capillary force, adhesion, and binding property can be expected due to the layered structure. That is, these new functions including improvement of hygroscopicity can be imparted by using phyllosilicate as fine particles.
  • phyllosilicate used in the present invention mica, sepiolite, montmorillonite, halosite, kaolinite, smectite, talc, vermiculite, chlorite, gyrolite, branite, silicic peacock, stone pebbles, fisheye stone, talc Pyrophyllite, chlorite, dickite, serpentine, zeolite and the like.
  • mica, talc, and kaolinite are more preferable in consideration of the particle diameter, aspect ratio, availability, and cost.
  • mica there are various types of mica depending on the shape and size, and examples include muscovite, chrome muscovite, sericite, biotite, phlogopite, fluorine phlogopite, and lithia mica.
  • Talc is also called talc and is a hydrate of magnesium silicate (Mg 3 Si 4 O 10 (OH) 2 ).
  • Kaolinite Al 2 Si 2 O 5 (OH) 4 , triclinic / monoclinic
  • Kaolinite Al 2 Si 2 O 5 (OH) 4 , triclinic / monoclinic
  • metal fine particles examples include nano metal particles such as gold, silver, platinum, palladium, ruthenium, copper, nickel, vanadium, titanium, indium, tin, and tungsten, and nano metal colloids.
  • the fine particles are mixed with water, methanol, ethanol, i-propanol, n-propanol, n-butanol, i-butanol, t-butanol, methoxyethanol, ethoxyethanol and other alcohols, ethylene glycol, acetate ester, carboxylic acid,
  • a suspension in which the fine particles are suspended is prepared using a general solvent such as lower hydrocarbon, aliphatic, aromatic, or a mixture thereof.
  • the method for supporting and immobilizing the fine particles on the network porous structure obtained in the first step is not particularly limited as long as the fine particles can be introduced.
  • the method for coating the suspension or the suspension is not particularly limited.
  • the method of impregnating a turbid liquid is mentioned.
  • wet coating can be performed by means of dip coating, flow coating, spray coating, plating, electroless plating, screen printing, flexographic printing, etc., and dip coating, spray coating, plating, no Electroplating is suitably used as a simple method.
  • Suspension coating can also be carried out dry, by applying a method in which the powder charged by the electrostatic coating method is made to collide with the oppositely charged sample for efficient adhesion, or the hydrophilic fine particles are applied at high speed by the blast method.
  • a method of spraying and finely coating the fine holes is preferably used.
  • Methods for impregnating the suspension include atmospheric pressure impregnation method, reduced pressure impregnation method, pressure impregnation method, sol-gel method, electrophoresis method, immersion ultrasonic impregnation method, etc.
  • a pressure impregnation method and an immersion ultrasonic parent method are preferably used.
  • the impregnation method using pressure reduction and pressurization is preferable.
  • an aluminum member having a network-like porous structure is placed in a suitable vacuum vessel, the pressure inside is reduced, and the suspension of the fine particles is introduced into the surface pores.
  • the fine particles can be densely packed. It is also possible to fill the container with more fine particles by introducing the suspension and then pressurizing the container.
  • the immersion ultrasonic method is also preferably used, and the fine particles are introduced while immersing the aluminum member in which the mesh-like porous structure is formed in the suspension and applying ultrasonic waves. Can be filled with fine particles.
  • the film After introducing the hydrophilic fine particles by coating or impregnation, the film can be formed by drying and heating, and the hydrophilic fine particles can be supported and fixed.
  • the drying / heating treatment method is not particularly limited, and may be dried at room temperature or may be heated and dried with hot air. Further, a method of heating the aluminum base material to 100 ° C. to 500 ° C. after drying and further drying is also used. For example, a method of drying at room temperature for 30 minutes and then heating in an oven at 150 ° C. for about 1 hour is used. In this way, an aluminum based composite hydrophilic member can be produced.
  • the pure water contact angle is desirably 30 degrees or less, as in the case of the hydrophilic member. This is because if the pure water contact angle exceeds 30 degrees, the predetermined hydrophilicity cannot be obtained. More preferably, it is 20 degrees or less, and more preferably 10 degrees or less.
  • the contact angle of pure water of the obtained composite hydrophilic member is measured, water droplets spread on the surface of the coating, and the contact angle is measured as 0 ° for convenience, and it can be observed that the coating is superhydrophilic.
  • the present inventors treated the aluminum-based material with a solution or suspension obtained by mixing “hydrophilic fine particles” with “basic mixed solution containing lithium hydroxide”, thereby forming a mesh-like porous material. It has been found that a hydrophilic member excellent in adhesion can be obtained in which hydrophilic fine particles are rapidly supported from the side on which the structure is formed, and the hydrophilic fine particles are more firmly supported by a simple process.
  • hydrophilic fine particles such as colloidal metal oxides and phyllosilicates react with alkali metal hydroxides, and there is a possibility of forming different forms of salts depending on the reaction.
  • Mixing and suspending hydrophilic fine particles in a basic mixed solution containing lithium hydroxide is a process that is not normally performed.
  • an aluminum-based hydrophilic member characterized in that a network-like porous structure is formed as a carrier on at least a part of the surface layer of aluminum or an alloy thereof, and the hydrophilic fine particles are supported and fixed on the carrier.
  • the hydrophilic fine particles are rapidly carried on the uneven surface of the porous body or inside the porous voids while the network-like porous structure is formed.
  • a hydrophilic member excellent in adhesiveness in which hydrophilic fine particles are more firmly supported is obtained.
  • aluminum material those described above are preferably used.
  • the mixed solvent is a mixture of the above-mentioned solvents, and the same adjusted material having the same properties is used, and hydrophilic fine particles are added thereto.
  • the particle diameter of the fine particles is not particularly limited, but is preferably in the range of 5 nm to 50 ⁇ m. If the average particle size is less than 5 nm, the particle size of the fine particles is too small, requiring a long coating time, resulting in poor efficiency. Also, the surface energy of the fine particles becomes very large, making monodispersion difficult and easy to aggregate. Is very difficult. On the other hand, if the average particle size of the fine particles exceeds 50 ⁇ m, the influence of gravity increases because the particle size is much larger than the pore size of the mesh-like porous structure on the coating, and the fine particles incorporated in the pore size cannot be retained. The problem of peeling off easily due to friction occurs. More preferably, it is 0.5 ⁇ m to 40 ⁇ m, and still more preferably 0.05 ⁇ m to 20 ⁇ m.
  • the particle size of the particles referred to here indicates the size of so-called primary particles, and does not indicate the size of secondary particles in which fine particles are aggregated.
  • the size of the secondary particles is not particularly limited as long as there is no difficulty in film formation.
  • the chemical solution for treating an aluminum material according to the present invention is a solution or suspension (hereinafter referred to as “fine particle mixed solution”) obtained by mixing the basic mixed solution and the hydrophilic fine particles.
  • the hydrophilic fine particles can be mixed as a hydrophilic sol.
  • the mixing amount of the hydrophilic fine particles is not particularly limited as long as it can be favorably supported on the porous body on which the fine particles are formed, but 0.01% by mass to 20% by mass with respect to the basic mixing liquid is appropriate. . If it is less than 0.01% by mass, it is too dilute and cannot be fully supported. If it is more than 20% by mass, the viscosity becomes too high and the operability is deteriorated. is there.
  • the prepared fine particle mixed solution desirably contains the hydrophilic fine particles contained therein uniformly in the basic mixed solution, and is preferably subjected to a treatment such as stirring or irradiation with ultrasonic waves.
  • the aluminum-based material when the aluminum-based material is treated with the fine particle mixed solution, the aluminum-based material needs to be brought into contact with the fine particle mixed solution.
  • the film removal treatment may be performed when the wettability with the chemical solution is poor.
  • surface activation treatment such as degreasing cleaning, sandpaper application, sandblasting, arc irradiation, plasma treatment, etc. is performed, but there are cases where uniform treatment is not possible due to unevenness during the surface activation treatment.
  • the hydrophilic member of the present invention the wettability with the aluminum surface is improved by lowering the surface tension of the fine particle mixture using an organic solvent, so that it is uniform regardless of unevenness during the surface treatment. It is possible to react.
  • the basic mixed solution containing lithium hydroxide has a certain degree of degreasing power, degreasing and surface activation treatment can be omitted by using the fine particle mixed solution.
  • the method of bringing the aluminum-based material into contact with the fine particle mixed solution is not particularly limited, but the method of spraying the fine particle mixed solution with a spray or the like, the method of dropping with a syringe, or the like (including impregnation) ), But a method of immersing in a treatment bath is preferably used.
  • Immersion can be performed under normal pressure, reduced pressure, or increased pressure.
  • an immersion ultrasonic method is also preferably used, and it is possible to immerse an aluminum material in a fine particle mixture and perform the treatment while applying ultrasonic waves.
  • the immersion time in the treatment bath may be selected appropriately depending on the type, shape and dimensions of the aluminum-based material and the concentration, composition, bath temperature, etc. of the fine particle mixture, and is usually set to 30 seconds to 15 minutes. Is done.
  • the bath temperature may be set to an appropriate temperature in consideration of the immersion time.
  • the fine particle mixed solution is set to room temperature to about 50 ° C., and more preferably 20 ° C. to 40 ° C. Set to ° C.
  • the temperature is lower than the above temperature range, the time required for the reaction to proceed is very long.
  • the temperature is high, the reaction becomes too fast, the coating is eroded violently, the mesh porous structure is destroyed, the surface Tends to be non-uniform.
  • the aluminum material and the basic mixing solution react to form a network-like porous structure having a pore diameter of 5 to 500 nm on the surface of the aluminum material.
  • the hydrophilic fine particles are supported as anchors so as to fit the pore size of the porous structure, and have both strong adhesion because the hydrophilic fine particles and the porous structure adhere to each other.
  • the said hydrophilic fine particle is carry
  • Some of the inorganic fine particles used have a particle diameter larger than 500 nm, but a strong bond is formed between the outermost surface portion of the inorganic fine particles that have entered the hole as an anchor and the larger inorganic fine particles. Therefore, it is considered that the fine particles in the pores hold the particles outside the membrane, form a complex surface, and are covered with a coating having a large specific surface area. Since the coating is composed of hydrophilic fine particles, it exhibits excellent hydrophilicity and is useful as an aluminum-based hydrophilic composite member.
  • the mass per unit area of the hydrophilic fine particles to be supported needs to be within the range of 0.1 g / m 2 to 20 g / m 2 . If the mass per unit area of the hydrophilic fine particles is less than 0.1 g / m 2 , it is not preferable because sufficient coating is not performed and unevenness occurs in the coating. On the other hand, when the mass of the hydrophilic fine particles exceeds 20 g / m 2 , the mesh-like porous material is covered with the fine powder over the entire surface, and the mesh-like porous material is completely buried to reduce the surface area, resulting in poor hydrophilicity. Not only economical, but it can be easily peeled off due to friction and vibration, causing a significant hindrance to mechanical strength.
  • the film can be formed by drying and heating, and hydrophilic fine particles can be supported and fixed.
  • the drying / heating treatment method is not particularly limited, and may be dried at room temperature or may be heated and dried with hot air. Further, a method of heating the aluminum base material to 100 ° C. to 500 ° C. after drying and further drying is also used. For example, a method of drying at room temperature for 30 minutes and then heating in an oven at 150 ° C. for about 1 hour is used. In this way, an aluminum based composite hydrophilic member can be produced.
  • the surface of the aluminum-based hydrophilic member obtained by the treatment of the present invention was observed with a scanning electron microscope. It was found that the fine particles were supported.
  • the pure water contact angle is desirably 30 degrees or less. This is because if the pure water contact angle exceeds 30 degrees, the predetermined hydrophilicity cannot be obtained. More preferably, it is 20 degrees or less, and more preferably 10 degrees or less.
  • the pure water contact angle is set to 30 degrees or less. For example, when the pure water contact angle is less than 5 degrees, high-precision measurement becomes difficult, but the hydrophilicity of the pure water contact angle is extremely close to 0 °. It is because the case where it shows is also included. In this specification, when a pure contact angle of 10 ° or less is exhibited, it is evaluated as “superhydrophilic”. The pure water contact angle is measured according to JIS R3257 “Testing method for wettability of substrate glass surface”.
  • the aluminum-based material was mixed with a base containing lithium hydroxide, water, and an organic solvent.
  • a basic mixed solution especially a basic mixed solution having a specific surface tension
  • the wettability with the surface of the aluminum-based material is improved, and a rapid reaction between the aluminum surface and lithium hydroxide proceeds. It was confirmed that a network-like porous structure different from the oxide film was formed on at least a part of the surface layer portion. Examples 1 to 6 are shown below.
  • Example 1 Aluminum plate (lithium hydroxide / water / EtOH system) Lithium hydroxide monohydrate (LiOH.H 2 O: Wako Special Grade Reagent) was weighed out in a 300 ml beaker, 6.0 g (0.14 mol) was added, and then 100 ml of ion-exchanged water was added and stirred at room temperature for dissolution. Further, 100 ml of special grade ethanol was gradually added with stirring to prepare a lithium hydroxide treatment solution having a concentration of 1.9% by mass. The pH of the treatment solution was 11.1.
  • a flat plate (thickness 0.1 mm, size 100 mm ⁇ 100 mm) of an aluminum base material A1050 having a purity of 99.5% by mass was immersed in a lithium hydroxide mixed solution prepared as described above at 25 ° C. . Fine hydrogen foaming was observed from the surface of the aluminum substrate 30 seconds after the immersion. After being immersed for about 1 minute, it was pulled up at 4 mm / sec and then dried at room temperature for 30 minutes. After drying, it was rinsed thoroughly with distilled water and dried again at room temperature. When the fine structure of the surface was observed with a scanning electron microscope, a uniform network fine structure was formed on the surface as shown in FIG.
  • Example 2 Aluminum plate (lithium hydroxide / water / MeOH system) 8.0 g (0.19 mol) of lithium hydroxide monohydrate (LiOH.H 2 O: Wako Special Grade Reagent) was weighed into a 300 ml beaker, and then 100 ml of ion exchange water was added and stirred at room temperature to dissolve. Further, 100 ml of special grade methanol was gradually added while stirring to prepare a lithium hydroxide treatment solution having a concentration of 2.5% by mass. The pH of the treatment solution was 11.3.
  • lithium hydroxide monohydrate LiOH.H 2 O: Wako Special Grade Reagent
  • a flat plate (thickness 0.1 mm, size 100 mm ⁇ 100 mm) of an aluminum base material A1050 having a purity of 99.5% by mass was immersed in a lithium hydroxide mixed solution prepared as described above at 25 ° C. . Fine hydrogen foaming was observed from the surface of the aluminum substrate 30 seconds after the immersion. After being immersed for about 1 minute, it was pulled up at 2 mm / sec and then dried at room temperature for 30 minutes. After drying, it was rinsed thoroughly with distilled water and dried again at room temperature. When the fine structure of the surface was observed with a scanning electron microscope, a uniform network fine structure was formed on the surface.
  • Example 3 Aluminum plate (lithium hydroxide / water / isopropanol system) Lithium hydroxide monohydrate (LiOH.H 2 O: Wako Special Grade Reagent) was weighed out in a 300 ml beaker by 5.0 g (0.12 mol), and then 140 ml of ion-exchanged water was added and stirred at room temperature for dissolution. Further, 60 ml of special grade isopropanol was gradually added with stirring to prepare a lithium hydroxide treatment solution having a concentration of 1.5% by mass. This solution was heated to 50 ° C. to prepare a treatment solution. The pH of the treatment liquid was 11.0.
  • an aluminum substrate having a purity of 99.5% by mass As an aluminum-based material, an aluminum substrate having a purity of 99.5% by mass: A 1050 flat plate (thickness 0.1 mm, size 100 mm ⁇ 100 mm) was immersed in the lithium hydroxide mixed solution prepared above at 50 ° C. Fine hydrogen foaming was observed from the surface of the aluminum substrate 20 seconds after the immersion. After being immersed for about 1 minute, it was pulled up at 5 mm / sec and then dried at room temperature for 20 minutes. After drying, it was rinsed thoroughly with distilled water and dried again at room temperature. When the surface microstructure was observed with an SEM, a uniform network microstructure was formed on the surface.
  • Example 4 Aluminum metal nonwoven fabric (lithium hydroxide / water / EtOH system) Prepared in Example 1 using an aluminum metal nonwoven fabric (trade name “METACILY”, manufactured by Thermal Corporation) having an average fiber diameter of 150 ⁇ m, a basis weight of 1.5 kg / m 2 , and a thickness of 1 mm as an aluminum-based material.
  • the said aluminum metal nonwoven fabric was immersed in the lithium hydroxide processing solution at 25 degreeC. Fine hydrogen foaming was observed from the surface of the aluminum substrate 30 seconds after the immersion, and after holding for about 1 minute, it was pulled up at 4 mm / sec and dried at room temperature for 30 minutes. When the fine structure of the surface was observed with a scanning electron microscope after thoroughly rinsing with distilled water after drying, a network fine structure with a uniform surface was formed (FIG. 2).
  • Example 5 Production of functional aluminum member (support of zeolite) Zeolite particles were supported by the immersion ultrasonic impregnation method on the aluminum metal nonwoven fabric having a mesh-like porous structure on the surface obtained in Example 4.
  • Example 4 In a 200 ml beaker, 5 g of Zeolum (manufactured by Tosoh Zeolum Co., Ltd.) was added, 100 ml of pure water was added, and the mixture was dispersed for 60 minutes with a UX-300 type ultrasonic disperser manufactured by Suntech Co., Ltd.
  • the aluminum metal nonwoven fabric having a network porous structure on the surface obtained in Example 4 was immersed in the suspension for 1 minute, then pulled up at 3 mm / sec and dried at 120 ° C. for 1 hour. When the surface microstructure was observed by SEM after drying, zeolite fine particles were uniformly embedded at 9.0 g / m 2 in the network porous structure as shown in FIG.
  • Example 6 The aldehyde adsorptivity test was conducted using the aluminum nonwoven fabric member obtained by embedding zeolite in the mesh porous structure formed on the surface and imparting the adsorptivity.
  • a. Test method The aluminum nonwoven fabric carrying the zeolite obtained in Example 5 was placed in a 10 L desiccator with a cock. The cock of the desiccator was opened and acetaldehyde was injected with a syringe to adjust the initial concentration to 150 ppm. When the concentration of acetaldehyde was measured as an initial value, it was 143 ppm. After 1 hour, gas was sampled from the cock and the concentration of acetaldehyde was measured.
  • Example 1 In the case of an aluminum plate (LiOH / water / water system) A lithium hydroxide aqueous solution having a concentration of 1.9% by mass was prepared in the same manner as in Example 1 except that water was used instead of special grade ethanol. did.
  • a flat plate (thickness 0.1 mm, size 100 mm ⁇ 100 mm) of an aluminum substrate A1050 having a purity of 99.5% by mass was placed in an aqueous lithium hydroxide solution having a concentration of 1.9% by mass at 25 ° C. It was immersed for 1 minute, then dried at room temperature for 30 minutes, washed with water, and re-dried at room temperature.
  • “Comparative Example 2” In the case of an aluminum plate (NaOH / EtOH / water system) Sodium hydroxide having a concentration of 1.9% by mass was obtained in the same manner as in Example 1 except that sodium hydroxide was used instead of lithium hydroxide. A / water / ethanol mixed solution was prepared. A flat plate (thickness 0.1 mm, size 100 mm ⁇ 100 mm) of an aluminum substrate A1050 having a concentration of 99.5% by mass was immersed in the mixed solution, and the same treatment as in Example 1 was performed. It was observed that the surface was visually changed to gray. When the surface state was observed with a scanning electron microscope, a fine porous body structure was not observed as shown in FIG. It seems that sodium hydroxide reacted violently with the aluminum surface as a strong alkali.
  • the aluminum-based material is treated with a basic mixed solution (particularly a basic mixed solution having a specific surface tension) in which a base containing lithium hydroxide, water, and an organic solvent are mixed. Improved wettability, and the rapid reaction between the aluminum surface and lithium hydroxide progressed, and a network-like porous structure different from the oxide film was formed on at least a part of the surface layer, and the hydrophilicity was remarkably improved. It was confirmed that a hydrophilic member was obtained and that the hydrophilic composite member obtained by further subjecting the hydrophilic member to hydrophilic treatment maintained good hydrophilicity.
  • a basic mixed solution particularly a basic mixed solution having a specific surface tension
  • a reticulated porous structure is formed by treating an aluminum-based material with a solution or suspension obtained by mixing “hydrophilic fine particles” with “basic mixed solution containing lithium hydroxide”. It was confirmed that a hydrophilic member excellent in adhesiveness in which hydrophilic fine particles were quickly supported from the side to be supported and the hydrophilic fine particles were more firmly supported by a simple process was obtained.
  • Example 7 hydrophilic member aluminum plate
  • the contact angle of the aluminum member after the treatment in Example 1 was measured, the water droplet spreads on the surface of the coating and became so small that the contact angle could not be measured (the contact angle was set to 0 degree for convenience), and the coating was superhydrophilic. I was able to observe something. Further, when the coating film was immersed in 1 L of water for 2 days and nights, the contact angle of pure water was measured again. As a result, the water droplets spread over the coating surface and became so small that the contact angle could not be measured (the contact angle was set to 0 degree for convenience). ), It was observed that the coating was superhydrophilic.
  • Example 8 Hydrophilic member: Aluminum mesh
  • the contact angle of the aluminum member after the treatment of Example 4 was measured, the water droplets spread on the surface of the coating and became so small that the contact angle could not be measured (contact for convenience) It was possible to observe that the coating was superhydrophilic. Further, when the coating film was immersed in 1 L of water for 2 days and nights, the contact angle of pure water was measured again. As a result, the water droplets spread over the coating surface and became so small that the contact angle could not be measured (the contact angle was set to 0 degree for convenience). ), It was observed that the coating was superhydrophilic.
  • Example 9 Composite hydrophilic member (aluminum plate / kaolinite) A hydrophilic member (aluminum plate) having a network-like porous structure obtained in the same manner as in Example 1 was immersed in a previously prepared suspension of hydrophilic fine particles (kaolinite), and an aluminum-based material was subjected to the following procedure. A composite hydrophilic member was produced and the water contact angle was measured.
  • kaolinite having an average particle size of 0.5 ⁇ m (manufactured by Takehara Chemical Industry Co., Ltd.) was weighed, 1000 ml of pure water was added, and the mixture was dispersed for 60 minutes with a UX-300 type ultrasonic dispersion machine manufactured by Suntech Co., Ltd.
  • a hydrophilic member (aluminum plate; 5 ⁇ 5 cm) having a mesh-like porous microstructure was immersed in 10 ml of this dispersion at room temperature while ultrasonically vibrating for 3 minutes, and pulled up at 5 mm / sec. This was dried at room temperature for 30 minutes, and then dried at 150 ° C. for 1 hour.
  • Kaolinite was uniformly applied on the surface of aluminum, and the mass per unit area of the film was 4.1 g / m 2 .
  • Example 10 Composite hydrophilic member (aluminum plate / colloidal silica)
  • the hydrophilic composite member (aluminum plate) having the network-like porous structure obtained in Example 1 is immersed in a preliminarily prepared suspension of hydrophilic fine particles (colloidal silica), and the aluminum-based composite hydrophilic member is prepared by the following procedure. Manufactured and measured water contact angle.
  • colloidal silica (trade name, IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) having an average particle size of 0.05 ⁇ m, add 100 ml of isopropanol, and use a UX-300 type ultrasonic dispersion machine manufactured by Suntech Co., Ltd. for 3 minutes. Dispersed.
  • a hydrophilic member (aluminum plate: 5 ⁇ 5 cm) having a mesh-like porous structure was immersed in 100 ml of this dispersion at room temperature while being ultrasonically vibrated for 3 minutes, and pulled up at 4 mm / sec. This was dried at room temperature for 30 minutes, and then dried at 150 ° C. for 1 hour.
  • colloidal silica was uniformly applied to the surface of aluminum as shown in FIG. The mass per unit area of the membrane was 2.2 g / m 2 .
  • Example 11 Composite hydrophilic member (aluminum mesh / colloidal silica) A hydrophilic member (aluminum mesh) having a network-like porous structure obtained in the same manner as in Example 8 was immersed in a preliminarily prepared hydrophilic fine particle (colloidal silica) suspension, and an aluminum-based material was subjected to the following procedure. A composite hydrophilic member was produced and the water contact angle was measured.
  • colloidal silica (trade name IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) with an average particle size of 0.05 ⁇ m, add 100 ml of isopropanol, and disperse for 3 minutes using a UX-300 type ultrasonic disperser manufactured by Suntech Co., Ltd. I let you.
  • a hydrophilic member (aluminum mesh) having a mesh-like porous structure obtained in the same manner as in Example 2 was immersed in 100 ml of this dispersion at room temperature while being ultrasonically vibrated for 3 minutes and pulled up at 5 mm / sec. It was. This was dried at room temperature for 30 minutes, and then dried at 150 ° C. for 1 hour. When observed with a scanning electron microscope, colloidal silica was uniformly coated on the surface of aluminum. The mass per unit area of the membrane was 6.3 g / m 2 .
  • Example 12 Composite hydrophilic member (aluminum plate / mica) It is immersed in a hydrophilic fine particle (mica) suspension prepared in advance in a hydrophilic member (aluminum plate) having a mesh-like porous structure obtained by the same method as in Example 1, and an aluminum-based composite hydrophilic property is obtained by the following procedure. A member was manufactured.
  • Dispersion obtained by taking 5 g of mica (trade name, A-11, manufactured by Yamaguchi Mica Co., Ltd.) having an average particle size of 3 ⁇ m, adding 100 ml of ethanol, and dispersing for 60 minutes using a UX-300 type ultrasonic disperser manufactured by Suntech Co., Ltd. The liquid was allowed to stand, and after 5 minutes, 50 ml of the supernatant was collected.
  • mica trade name, A-11, manufactured by Yamaguchi Mica Co., Ltd.
  • UX-300 type ultrasonic disperser manufactured by Suntech Co., Ltd.
  • a hydrophilic member (aluminum plate: 5 ⁇ 5 cm) having a mesh-like porous fine structure at room temperature was immersed in the dispersion while being ultrasonically vibrated for 3 minutes, and pulled up at 3 mm / sec. This was dried at room temperature for 30 minutes, and then dried at 150 ° C. for 1 hour. Mica was uniformly applied to the surface of aluminum, and the mass per unit area of the film was 9.3 g / m 2 .
  • the contact angle of pure water was measured, the contact angle was 5.1 degrees immediately after dropping, but within 1 minute, the water droplets spread on the surface of the coating and became so small that the contact angle could not be measured (for convenience, the contact angle was reduced). It was observed that the coating was superhydrophilic.
  • the pure water contact angle was measured after washing with clean water for 3 minutes, the pure water contact angle was 0 ° and no change in hydrophilicity was observed.
  • Example 13 Composite hydrophilic member (aluminum plate / silver particles / mica) A hydrophilic member (aluminum plate) having a mesh-like porous structure obtained in the same manner as in Example 1 was immersed in a suspension of previously prepared hydrophilic fine particles (silver particles / mica) and aluminum was obtained by the following procedure. A system composite hydrophilic member was produced, and a pure water contact angle was measured.
  • Example 14 Composite hydrophilic member (aluminum plate / scallop calcined shell calcium) A hydrophilic member (aluminum / plate) having a mesh-like porous structure obtained by the same method as in Example 1 was immersed in a suspension of previously prepared hydrophilic fine particles (scallop calcined calcium shell) and aluminum was obtained in the following procedure. A system composite hydrophilic member was produced, and a pure water contact angle was measured.
  • the aluminum-based material is processed using a solution or suspension obtained by mixing “hydrophilic fine particles” with “basic mixed solution containing lithium hydroxide” to form a network-like porous structure. It was confirmed that a hydrophilic member excellent in adhesiveness in which hydrophilic fine particles were quickly supported from the side to be supported and the hydrophilic fine particles were more firmly supported by a simple process was obtained.
  • Example 15 Hydrophilic member: aluminum plate Lithium hydroxide monohydrate (LiOH.H 2 O: Wako Special Grade Reagent) was weighed out in a 300 ml beaker, 6.0 g (0.14 mol) was added, and then 100 ml of ion-exchanged water was added and stirred at room temperature for dissolution. Further, 100 ml of special grade ethanol was gradually added with stirring to prepare a lithium hydroxide treatment solution having a concentration of 1.9% by mass. The pH of the treatment solution was 11.1.
  • kaolinite manufactured by Takehara Chemical Industry Co., Ltd.
  • UX-300 type ultrasonic disperser manufactured by Suntech Co.
  • a fine particle mixed solution was dispersed.
  • a flat plate (thickness 0.1 mm, size 100 mm ⁇ 50 mm) of an aluminum base material: A1050 having a purity of 99.5% by mass was immersed in this fine particle mixture while being ultrasonically vibrated at room temperature. Fine hydrogen foaming was observed from the surface of the aluminum substrate 30 seconds after the immersion. After dipping for about 1 minute, the film was pulled up at 4 mm / sec, then dried at room temperature for 30 minutes, and dried at 150 ° C. for 1 hour. Kaolinite was uniformly applied on the surface of aluminum, and the mass per unit area of the film was 4.1 g / m 2 .
  • Example 16 A hydrophilic member was produced in the same manner as in Example 1 except that colloidal silica was used as the hydrophilic fine particles.
  • colloidal silica (trade name, IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) having an average particle size of 0.05 ⁇ m as hydrophilic fine particles was added to a basic mixed solution prepared in the same manner as in Example 15, and Suntech Co., Ltd. The mixture was dispersed with a UX-300 type ultrasonic dispersing machine for 20 minutes to prepare a white milky color fine particle mixture.
  • an A1050 flat plate (thickness 0.1 mm, size 100 mm ⁇ 50 mm) as an aluminum substrate having a purity of 99.5% by mass was immersed while being ultrasonically vibrated at room temperature. Fine hydrogen foaming was observed from the surface of the aluminum substrate 30 seconds after the immersion. After being immersed for about 1 minute, it was pulled up at 4 mm / sec, then dried at room temperature for 30 minutes, and dried at 150 ° C. for 1 hour. According to SEM observation, 50% of the voids in the porous aluminum body were filled with colloidal silica. Although the carrying amount decreased by 42% compared to the conventional method treated in the two-step process, the hydrophilicity was not changed at all, and the pure water contact angle was 4.5 degrees.
  • Example 17 A hydrophilic member was produced in the same manner as in Example 15 except that calcined shell calcium was used as the hydrophilic fine particles.
  • a flat plate (thickness 0.1 mm, size 100 mm ⁇ 50 mm) of an aluminum base material A1050 having a purity of 99.5% by mass was immersed in this fine particle mixture while being ultrasonically vibrated at room temperature. Fine hydrogen foaming was observed from the surface of the aluminum substrate 30 seconds after the immersion. After being immersed for about 1 minute, it was pulled up at 4 mm / sec, then dried at room temperature for 30 minutes, and dried at 150 ° C. for 1 hour.
  • the aluminum network porous structure of the present invention is useful as a carrier, and supports fine particles having a catalyst, a dye, adsorptivity, hydrophilicity, and water repellency in the porous body. It is useful as a functional material having the function by immobilization. For example, by supporting and fixing superhydrophilic fine particles as functional fine particles, the mesh-like porous structure becomes a hydrophilic member exhibiting superhydrophilic properties, and is useful as a member of heat exchange elements such as heat pipes and fins. Be utilized.

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Abstract

Disclosed is a porous network structure in which the matrix comprises aluminum or an alloy thereof and at least a part of the surface layer is treated by a basic mixed solution which comprises a base comprising lithium hydroxide, water and an organic solvent. The porous network structure is characterized by having pores each having a pore diameter of 5 to 500 nm and a depth of 0.05 to 10 μm. The porous network structure is useful as a carrier for microparticles. A functional member can be produced by supporting and immobilizing functional microparticles on the porous network structure. Particularly, when the functional microparticles are hydrophilic, a hydrophilic member can be produced.

Description

網目状多孔質構造体およびそれを用いた親水性部材およびこれらの製造方法Reticulated porous structure, hydrophilic member using the same, and production method thereof
本発明は、アルミニウムもしくはその合金の表面に形成させた網目状多孔質構造体および当該網目状多孔質構造体に親水性処理を施した親水性部材、およびこれらの製造方法に関する。 The present invention relates to a mesh-like porous structure formed on the surface of aluminum or an alloy thereof, a hydrophilic member obtained by subjecting the mesh-like porous structure to a hydrophilic treatment, and a method for producing the same.
発明の背景Background of the Invention
　アルミニウムもしくはその合金（以下、総称して「アルミニウム系」とする）に表面処理を行って細孔を形成する方法として、一般に、硫酸やシュウ酸の水溶液を電解浴としてアルミニウム等の表面に陽極酸化被膜を形成させる、いわゆる「アルマイト処理」が行われている（特許文献１）。このアルマイト処理は、細孔を有する耐食性の厚い被膜が得られる反面、工程が複雑で、しかも設備費および電力コストが高いという問題がある。また、アルマイト処理においては１０ｎｍ～２０ｎｍの細孔が形成されるものの、表面積が大きくない。 As a method of forming pores by performing surface treatment on aluminum or its alloys (hereinafter collectively referred to as “aluminum-based”), anodization is generally performed on the surface of aluminum or the like using an aqueous solution of sulfuric acid or oxalic acid as an electrolytic bath. So-called “alumite treatment” for forming a film is performed (Patent Document 1). Although this alumite treatment can provide a corrosion-resistant thick film having pores, it has a problem that the process is complicated and that the equipment cost and the power cost are high. Further, in the alumite treatment, although pores of 10 nm to 20 nm are formed, the surface area is not large.
　そのため、処理液に浸漬するだけで被膜形成ができ、工程、設備が比較的簡単で処理コストが安い化学的処理の利用が望ましい。そこで、このような化学的処理として、例えば、アミン溶液にアルミニウム等を浸漬後、熱水処理することにより、表面に水和酸化被膜を形成させる、いわゆる「ベーマイト法」による処理が行われ、特許文献２等に開示されている。「ベーマイト法」による表面処理は、アルミニウムあるいはその合金に被膜を形成させ耐食性を高めることを目的にしている。 Therefore, it is desirable to use a chemical treatment that can form a film only by immersing in a treatment solution, has a relatively simple process and equipment, and has a low treatment cost. Therefore, as such chemical treatment, for example, a so-called “boehmite method” is performed in which a hydrated oxide film is formed on the surface by hot water treatment after immersing aluminum or the like in an amine solution. It is disclosed in Document 2 and the like. The surface treatment by the “boehmite method” is intended to improve corrosion resistance by forming a film on aluminum or its alloy.
　一方、アルミニウム表面を、リチウムイオンを含む水酸化アルカリで処理することにより被膜を形成させる表面処理方法として、硝酸リチウムと苛性ソーダの水溶液にアルミニウム素材を浸漬させる方法が特許文献３に開示され、リチウムイオンと炭酸イオンを含むアルカリ溶液でアルミニウム表面を処理する方法が特許文献４に開示され、これらの方法によりアルミニウム表面に被膜が形成される。 On the other hand, Patent Document 3 discloses a method of immersing an aluminum material in an aqueous solution of lithium nitrate and caustic soda as a surface treatment method for forming a film by treating an aluminum surface with an alkali hydroxide containing lithium ions. Patent Document 4 discloses a method of treating an aluminum surface with an alkaline solution containing carbon dioxide and carbon dioxide, and a film is formed on the aluminum surface by these methods.
また、金属の表面に親水性を付与することにより、水等の極性液体と物品との親和性が向上するため、親水性の被覆層と基材とを有する親水性部材は、水等の極性液体と接する環境にて、当該親和性を活用した防汚性物品、結露防止性物品、極性液体の循環性を向上させた物品等として利用される。これら応用分野の具体例として、ヒートパイプ、フィン等の熱交換素子用の部材が挙げられる。 In addition, since hydrophilicity is imparted to the surface of the metal to improve the affinity between the polar liquid such as water and the article, the hydrophilic member having the hydrophilic coating layer and the substrate has polarity such as water. In an environment in contact with a liquid, it is used as an antifouling article utilizing the affinity, an anti-condensation article, an article with improved polar liquid circulation, and the like. Specific examples of these application fields include members for heat exchange elements such as heat pipes and fins.
特にアルミニウムの基材に関して親水性を向上させる方法としては、アルミニウム表面に成膜処理を施すか、塗装処理が行われるのが一般的であり、以下のような方法が知られている。
（１）リチウム塩存在下、アルミニウム合金を、アミン類を含有する熱水または水蒸気に接触させるベーマイト処理を行う工程（特許文献２に開示）。
（２）アルミニウム表面をアルカリシリケート（アルカリ金属ケイ酸塩）と無機硬化剤と水溶性有機高分子化合物を含む溶液でコーティングすることにより親水性被膜を形成する方法（特許文献５に開示）
（３）アルミニウムからなる部品の表面に、シラノール基を有する化合物とポリビニルピロリドンを含有する水性媒体中に浸漬することによる親水性付与の方法（特許文献６に開示）
（４）クロメート処理を施し、つぎに正リン酸を含むアルカリシリケート（アルカリ金属ケイ酸塩）水溶液を塗布した後、さらに正リン酸溶液を塗布し、しかる後加熱乾燥することによる親水性被膜形成方法（特許文献７に開示） In particular, as a method for improving the hydrophilicity with respect to an aluminum base material, a film forming process or a coating process is generally performed on the aluminum surface, and the following methods are known.
(1) A step of performing a boehmite treatment in which an aluminum alloy is brought into contact with hot water or steam containing amines in the presence of a lithium salt (disclosed in Patent Document 2).
(2) A method of forming a hydrophilic film by coating an aluminum surface with a solution containing an alkali silicate (alkali metal silicate), an inorganic curing agent, and a water-soluble organic polymer compound (disclosed in Patent Document 5)
(3) A method of imparting hydrophilicity by immersing in an aqueous medium containing a compound having a silanol group and polyvinylpyrrolidone on the surface of a part made of aluminum (disclosed in Patent Document 6)
(4) Applying a chromate treatment and then applying an aqueous solution of alkali silicate (alkali metal silicate) containing normal phosphoric acid, then applying a normal phosphoric acid solution, and then heating and drying to form a hydrophilic film Method (disclosed in Patent Document 7)
特開２００６－３２８４６７号公報JP 2006-328467 A 特開昭５２－９６４２号公報JP 52-9642 A 特開昭４８－１８１３１号公報Japanese Patent Laid-Open No. 48-18131 特開２００５－８９４９号公報JP 2005-8949 A 特開昭６２－２３５４７７号公報JP-A-62-235477 特開昭６２－２７２０９９号公報JP-A-62-272099 特開平１－２０８４７５号公報Japanese Patent Laid-Open No. 1-208475
　上記ベーマイト法による処理は、アルマイト処理と比べて工程・設備が簡単であり、処理コストも安く、省エネルギーの点でも有利であるものの、熱水処理を行う工程が必要であり製造に手間がかかる他、被膜の形成が必ずしも規則正しいものではなく、網目状多孔質構造体は得られない。 The treatment by the boehmite method is simpler in process and equipment than the alumite treatment, is cheaper in processing cost, and is advantageous in terms of energy saving, but requires a hot water treatment step and takes time to manufacture. The formation of the film is not always regular, and a reticulated porous structure cannot be obtained.
　同様に、特許文献３または特許文献４に記載の方法では、水和酸化アルミニウムの被膜が得られるとの記載はあるものの網目状多孔質構造体についての記載はない。 Similarly, the method described in Patent Document 3 or Patent Document 4 describes that a hydrated aluminum oxide film can be obtained, but does not describe a mesh-like porous structure.
　このように、従来法によるアルミニウムの表面処理においては、数ｎｍ～数１００ｎｍレベルの孔径であり、かつ表面積の大きい多孔質構造体は作りえず、簡便な方法で得られる当該構造体およびその製造方法が求められていた。 As described above, in the surface treatment of aluminum by the conventional method, a porous structure having a pore diameter of several nanometers to several hundred nanometers and a large surface area cannot be produced, and the structure obtained by a simple method and its production A method was sought.
　本発明は、このような事情に鑑みなされたもので、化学的処理により、アルミニウムもしくはその合金の表層部の少なくとも一部に形成される網目多孔質構造体およびその製造方法の提供を目的とする。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide a network porous structure formed on at least a part of a surface layer portion of aluminum or an alloy thereof by a chemical treatment and a method for producing the same. .
　また、上記特許文献５および特許文献７に記載の方法は、アルカリシリケート（アルカリ金属ケイ酸塩）を利用しての親水性を付与するものであるが、部材と物理的に付着しているので密着性が必ずしも十分とはいえない。しかも、アルカリシリケートの強固な膜を形成させようとすると４００℃とかなり高温で処理する必要があるため工業的な手法とはいいがたく、１２０℃～１５０℃程度の比較的低温で処理した場合においては硬化が充分でなく、アルカリシリケート由来の親水性被膜を長時間にわたり水と接触させた場合、被膜中の親水性の部位が徐々に消滅するという問題を生じることがある。また、特許文献６に記載の方法は、充分な親水性が得られないため問題がある。さらに、特許文献２、特許文献３および特許文献４に記載の方法では、水和酸化アルミニウムの被膜が得られるとの記載があるが、当該被膜は経時とともに親水性が低下していくことが知られている。 Moreover, although the method of the said patent document 5 and the patent document 7 provides hydrophilicity using an alkali silicate (alkali metal silicate), since it has adhered physically to the member. Adhesion is not always sufficient. In addition, if an alkali silicate strong film is to be formed, it is necessary to treat at a fairly high temperature of 400 ° C., so this is not an industrial technique, and in the case of treatment at a relatively low temperature of about 120 ° C. to 150 ° C. Is not sufficiently cured, and when a hydrophilic coating derived from an alkali silicate is brought into contact with water for a long time, there may be a problem that the hydrophilic portion in the coating gradually disappears. Further, the method described in Patent Document 6 has a problem because sufficient hydrophilicity cannot be obtained. Furthermore, the methods described in Patent Document 2, Patent Document 3 and Patent Document 4 describe that a coating of hydrated aluminum oxide is obtained, but it is known that the hydrophilicity of the coating decreases with time. It has been.
したがって、簡便な化学的処理により、アルミニウムもしくはその合金の表層部を処理して形成した細孔を有する部材に親水性を付与し、親水性および密着性に優れる部材およびその製造方法が求められていた。 Therefore, there is a need for a member that has hydrophilicity and adhesion, and a method for producing the same, by imparting hydrophilicity to a member having pores formed by treating the surface layer of aluminum or an alloy thereof by simple chemical treatment. It was.
本発明は、かかる課題を解決することを目的とする。 The present invention aims to solve this problem.
本発明者らは、上記問題を解決するために、アルミニウム系材料に化学的な処理を施し、細孔を形成させることを目的として一連の研究を重ねる過程で、アルミニウム系材料を、水酸化リチウムを含む塩基と水と有機溶媒を混合した塩基性混合溶液（特に特定の表面張力を有する塩基性混合溶液）で表面処理することにより、アルミニウム系材料の表面との濡れ性が改善され、アルミニウム表面と水酸化リチウムの速やかな反応が進行して、表層部の少なくとも一部に酸化被膜とは異なる網目状多孔質構造体が形成されることを見出し本発明に到達した。 In order to solve the above-mentioned problems, the inventors of the present invention have made a series of studies for the purpose of chemically treating an aluminum-based material and forming pores. Surface treatment with a basic mixed solution (especially a basic mixed solution having a specific surface tension) in which water and an organic solvent are mixed to improve the wettability with the surface of an aluminum-based material. As a result, the inventors have found that a network-like porous structure different from the oxide film is formed on at least a part of the surface layer portion by the rapid reaction between lithium hydroxide and lithium hydroxide.
次いで、アルミニウム系材料を、水酸化リチウムを含む塩基と水と有機溶媒を混合した塩基性混合溶液（特に特定の表面張力を有する塩基性混合溶液）で処理することにより、アルミニウム系材料の表面との濡れ性が改善され、アルミニウム表面と水酸化リチウムの速やかな反応が進行して、表層部の少なくとも一部に酸化被膜とは異なる網目状多孔質構造体が形成され、親水性が著しく向上した親水性部材が得られることを見出し本発明に到達した。また、当該親水性部材に対してさらに親水性処理を施した親水性複合部材についても良好な親水性を維持することが認められた。 Next, the aluminum-based material is treated with a basic mixed solution (particularly a basic mixed solution having a specific surface tension) in which a base containing lithium hydroxide, water, and an organic solvent are mixed. Improved wettability, and the rapid reaction between the aluminum surface and lithium hydroxide progressed, and a network-like porous structure different from the oxide film was formed on at least a part of the surface layer, and the hydrophilicity was remarkably improved. The inventors have found that a hydrophilic member can be obtained and have reached the present invention. In addition, it was confirmed that the hydrophilic composite member obtained by further subjecting the hydrophilic member to hydrophilic treatment maintains good hydrophilicity.
　また、「水酸化リチウムを含む塩基性混合溶液」に「親水性微粒子」を混合してなる溶液または懸濁液を用いてアルミニウム系材料を処理することにより、網目状多孔質構造体が形成される側から親水性微粒子が速やかに担持され、簡単なプロセスにより親水性微粒子がより強固に担持された密着性に優れる親水性部材が得られることを見出した。 In addition, a reticulated porous structure is formed by treating an aluminum material with a solution or suspension obtained by mixing “hydrophilic fine particles” with “basic mixed solution containing lithium hydroxide”. It was found that a hydrophilic member excellent in adhesiveness in which hydrophilic fine particles are rapidly supported from the side to be supported and hydrophilic fine particles are more firmly supported by a simple process can be obtained.
なお、コロイダル金属酸化物やフィロ珪酸塩等の親水性微粒子は、アルカリ金属の水酸化物と反応することは当業者にも知られており、反応により形態の違う塩を形成する可能性もあり、親水性微粒子を水酸化リチウムを含む塩基性混合溶液に混合懸濁させることは通常は行われないプロセスである。 In addition, it is known to those skilled in the art that hydrophilic fine particles such as colloidal metal oxides and phyllosilicates react with alkali metal hydroxides, and there is a possibility of forming different forms of salts depending on the reaction. Mixing and suspending hydrophilic fine particles in a basic mixed solution containing lithium hydroxide is a process that is not normally performed.
以下に、課題を解決する手段について、順を追って示す。 The means for solving the problem will be described below in order.
最初に、本発明者らは、アルミニウム系材料に化学的な処理を施し、細孔を形成させることを目的として一連の研究を重ねる過程で、アルミニウム系材料を、水酸化リチウムを含む塩基と水と有機溶媒を混合した塩基性混合溶液（特に特定の表面張力を有する塩基性混合溶液）で処理することにより、アルミニウム系材料の表面との濡れ性が改善され、アルミニウム表面と水酸化リチウムの速やかな反応が進行して、表層部の少なくとも一部に酸化被膜とは異なる網目状多孔質構造体が形成されることを見出し本発明に到達した。また、当該網目状多孔質構造体を担体として機能性微粒子を担持固定することにより、容易にアルミニウム系機能性部材を製造しうることを見出した。 First, in the process of conducting a series of studies for the purpose of chemically treating an aluminum-based material and forming pores, the inventors have made the aluminum-based material a base containing lithium hydroxide and water. By treating with a basic mixed solution (especially a basic mixed solution having a specific surface tension) mixed with an organic solvent, the wettability with the surface of the aluminum-based material is improved. As a result of this reaction, it was found that a network-like porous structure different from the oxide film was formed on at least a part of the surface layer portion, and the present invention was reached. Further, it has been found that an aluminum-based functional member can be easily produced by supporting and fixing functional fine particles using the network porous structure as a carrier.
即ち、本発明において、母材がアルミニウムもしくはその合金からなり、表層部の少なくとも一部を、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液で処理して形成した網目状多孔質構造体であって、当該網目状多孔質構造体が、孔径５ｎｍ～５００ｎｍ、深さ０．０μｍ５～１０μｍの細孔を含むことを特徴とする網目状多孔質構造体が得られ、当該網目状多孔質構造体は微粒子の担体として有用であり、機能性を有する微粒子を担持固定させることにより、機能性部材を製造できる。 That is, in the present invention, the base material is made of aluminum or an alloy thereof, and at least a part of the surface layer is formed by treating with a basic mixed solution in which a base containing lithium hydroxide, water, and an organic solvent are mixed. A mesh-like porous structure, characterized in that the mesh-like porous structure comprises pores having a pore diameter of 5 nm to 500 nm and a depth of 0.0 μm to 5 μm, The network porous structure is useful as a carrier for fine particles, and a functional member can be produced by supporting and fixing fine particles having functionality.
即ち、本発明は、以下の発明１～発明５を含む。 That is, the present invention includes the following inventions 1 to 5.
「発明１」 
母材がアルミニウムもしくはその合金からなり、表層部の少なくとも一部を、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液で接触処理して形成した網目状多孔質構造体であって、当該網目状多孔質構造が、孔径５ｎｍ～５００ｎｍ、深さ０．０５μｍ～１０μｍの範囲内の細孔を含むことを特徴とする網目状多孔質構造体。 "Invention 1"
A network-like porous structure formed by contact treatment of at least part of the surface layer portion with a basic mixed solution in which a base containing lithium hydroxide, water and an organic solvent are mixed, the base material being made of aluminum or an alloy thereof. A reticulated porous structure, wherein the reticulated porous structure includes pores having a pore diameter of 5 nm to 500 nm and a depth of 0.05 μm to 10 μm.
「発明２」 
アルミニウムもしくはその合金を、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液で接触処理することにより、アルミニウムもしくはその合金の表層部の少なくとも一部に、網目状多孔質の細孔を形成することを特徴とする網目状多孔質構造体の製造方法。 "Invention 2"
By subjecting aluminum or an alloy thereof to a contact treatment with a basic mixed solution in which a base containing lithium hydroxide, water, and an organic solvent are mixed, at least a part of the surface layer portion of aluminum or the alloy has a mesh-like porous structure. A method for producing a reticulated porous structure, wherein pores are formed.
「発明３」
塩基性混合溶液を構成する混合溶媒の表面張力が、１８ｍＮ／ｍ～６０ｍＮ／ｍの範囲内にあることを特徴とする発明２に記載のアルミニウム系親水性部材の製造方法。 "Invention 3"
3. The method for producing an aluminum-based hydrophilic member according to invention 2, wherein the mixed solvent constituting the basic mixed solution has a surface tension in the range of 18 mN / m to 60 mN / m.
「発明４」
塩基性混合溶液中の有機溶媒が、アルコール系、ニトリル系、ケトン系、エステル系、エーテル系、スルホキシド系、アミド系、グリコール系、芳香族系もしくは、含フッ素アルコール系の溶媒の少なくとも一種である発明２または発明３に記載の網目状多孔質構造体の製造方法。 "Invention 4"
The organic solvent in the basic mixed solution is at least one of an alcohol, nitrile, ketone, ester, ether, sulfoxide, amide, glycol, aromatic, or fluorinated alcohol solvent. A method for producing a reticulated porous structure according to invention 2 or invention 3.
「発明５」
　塩基性混合溶液のｐＨが、９．０～１３．５の範囲内にあることを特徴とする発明２乃至発明４のいずれか１つに記載の網目状多孔質構造体の製造方法。 "Invention 5"
The method for producing a reticulated porous structure according to any one of Inventions 2 to 4, wherein the pH of the basic mixed solution is in the range of 9.0 to 13.5.
次いで、本発明者らは、アルミニウム系材料に様々な化学的な処理を施して細孔を形成させることにより、親水性を向上させることを目的として一連の研究の過程でアルミニウム系材料を、水酸化リチウムを含む塩基と水と有機溶媒を混合した塩基性混合溶液（特に特定の表面張力を有する塩基性混合溶液）で処理することにより、アルミニウム系材料の表面との濡れ性が改善され、アルミニウム表面と水酸化リチウムの速やかな反応が進行して、表層部の少なくとも一部に酸化被膜とは異なる網目状多孔質構造体が形成され、親水性が著しく向上した親水性部材が得られることを見出し本発明に到達した。また、当該親水性部材に対してさらに親水性処理を施した親水性複合部材についても良好な親水性を維持することが認められた。 Next, the present inventors performed various chemical treatments on the aluminum-based material to form pores, thereby improving the hydrophilicity in the course of a series of studies, By treating with a basic mixed solution (particularly a basic mixed solution having a specific surface tension) in which a base containing lithium oxide, water, and an organic solvent are mixed, the wettability with the surface of the aluminum-based material is improved. A rapid reaction between the surface and lithium hydroxide proceeds, and a network-like porous structure different from the oxide film is formed on at least a part of the surface layer portion, thereby obtaining a hydrophilic member with significantly improved hydrophilicity. The present invention has been reached. In addition, it was confirmed that the hydrophilic composite member obtained by further subjecting the hydrophilic member to hydrophilic treatment maintains good hydrophilicity.
即ち、本発明において、アルミニウム系親水性部材は、少なくとも水酸化リチウムを含む塩基と水と有機溶媒を混合した塩基性混合溶液でアルミニウム系材料を処理することにより、アルミニウム系材料の表面の少なくとも一部に網目状多孔質構造体を形成させる（第一工程）。第一工程で得られたアルミニウム系親水部材の網目状多孔質構造を担体として利用してさらなる親水性処理（第二工程）を施すことにより、機能性を有したアルミニウム系複合親水性部材が製造できる。 That is, in the present invention, the aluminum-based hydrophilic member is obtained by treating the aluminum-based material with a basic mixed solution obtained by mixing a base containing at least lithium hydroxide, water, and an organic solvent, thereby at least one surface of the aluminum-based material. A mesh-like porous structure is formed on the part (first step). By using the network porous structure of the aluminum-based hydrophilic member obtained in the first step as a carrier, further hydrophilic treatment (second step) is performed to produce an aluminum-based composite hydrophilic member having functionality. it can.
即ち、本発明は、以下の発明６～発明１４を含む。 That is, the present invention includes the following invention 6 to invention 14.
「発明６」 
母材がアルミニウムもしくはその合金からなり、表層部の少なくとも一部を、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液で接触処理して形成した網目状多孔質構造体を有するアルミニウム系親水性部材であって、当該網目状多孔質構造体が、孔径５ｎｍ～５００ｎｍ、深さ０．０５μｍ～１０μｍの範囲内の細孔を含むことを特徴とするアルミニウム系親水性部材。 "Invention 6"
A network-like porous structure formed by contact treatment of at least part of the surface layer portion with a basic mixed solution in which a base containing lithium hydroxide, water and an organic solvent are mixed, the base material being made of aluminum or an alloy thereof. An aluminum-based hydrophilic member, characterized in that the network porous structure includes pores having a pore diameter of 5 nm to 500 nm and a depth of 0.05 μm to 10 μm. .
「発明７」 
下記、第一工程よりなるアルミニウム系親水性部材の製造方法。
第一工程：アルミニウムもしくはその合金を、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液で接触処理することにより、アルミニウムもしくはその合金の表層部の少なくとも一部に、網目状多孔質の細孔を形成する工程。 "Invention 7"
The manufacturing method of the aluminum-type hydrophilic member which consists of the following and 1st processes.
First step: By subjecting aluminum or an alloy thereof to contact treatment with a basic mixed solution in which a base containing lithium hydroxide, water and an organic solvent are mixed, at least a part of the surface layer of aluminum or an alloy thereof is meshed. Forming a fine porous pore.
「発明８」　
塩基性混合溶液を構成する混合溶媒の表面張力が、１８ｍＮ／ｍ～６０ｍＮ／ｍの範囲内にあることを特徴とする発明７に記載のアルミニウム系親水性部材の製造方法。 "Invention 8"
8. The method for producing an aluminum-based hydrophilic member according to invention 7, wherein the surface tension of the mixed solvent constituting the basic mixed solution is in the range of 18 mN / m to 60 mN / m.
「発明９」　
塩基性混合溶液中の有機溶媒が、アルコール系、ニトリル系、ケトン系、エステル系、エーテル系、スルホキシド系、アミド系、グリコール系、芳香族系もしくは、含フッ素アルコール系の溶媒の少なくとも一種である発明７または発明８に記載のアルミニウム系親水性部材の製造方法。 "Invention 9"
The organic solvent in the basic mixed solution is at least one of an alcohol, nitrile, ketone, ester, ether, sulfoxide, amide, glycol, aromatic, or fluorinated alcohol solvent. The manufacturing method of the aluminum-type hydrophilic member of the invention 7 or the invention 8.
「発明１０」　
塩基性混合溶液のｐＨが、９．０～１３．５の範囲内にあることを特徴とする発明７乃至発明９のいずれか１つに記載のアルミニウム系親水性部材の製造方法。 "Invention 10"
The method for producing an aluminum-based hydrophilic member according to any one of Inventions 7 to 9, wherein the pH of the basic mixed solution is in the range of 9.0 to 13.5.
「発明１１」　
第一工程で得られた網目状多孔質構造を有する親水性部材の多孔質構造部位を担体として、親水性の微粒子を担持固定せしめる第二工程を施すことを特徴とする発明７乃至発明１０のいずれか１つに記載のアルミニウム系複合親水性部材の製造方法。 "Invention 11"
Invention 7 thru | or Invention 10 characterized by performing the 2nd process of carrying and fixing hydrophilic microparticles using the porous structure part of the hydrophilic member which has the network porous structure obtained at the 1st process as a carrier. The manufacturing method of the aluminum type composite hydrophilic member as described in any one.
「発明１２」　
親水性の微粒子がコロイダルシリカ、コロイダルアルミナ、コロイド状のチタニア、ゼオライト、シリカゲル、シリカ、アルミナ、チタニア、炭酸カルシウム、酸化カルシウム、タルク、珪藻土、バーミキュライト、ヒル石、弁柄、貝殻焼成カルシウムの微粒子、または、金、銀、白金、パラジウム、ルテニウム、銅、ニッケル、バナジウム、チタン、インジウム、スズ、タングステンのナノ金属粒子もしくはナノ金属コロイドよりなる群より選ばれる少なくとも一つである発明１１に記載のアルミニウム系複合親水性部材の製造方法。 "Invention 12"
Hydrophilic fine particles are colloidal silica, colloidal alumina, colloidal titania, zeolite, silica gel, silica, alumina, titania, calcium carbonate, calcium oxide, talc, diatomaceous earth, vermiculite, vermiculite, petal, shell calcined calcium fine particles, Alternatively, the aluminum according to invention 11, which is at least one selected from the group consisting of nanometal particles or nanometal colloids of gold, silver, platinum, palladium, ruthenium, copper, nickel, vanadium, titanium, indium, tin, and tungsten. Of producing a composite composite hydrophilic member.
「発明１３」　
第二工程において、親水性微粒子の質量が０．１ｇ／ｍ2～２０ｇ／ｍ2の範囲内になるように担持させることを特徴とする発明１１または発明１２に記載のアルミニウム系複合親水性部材の製造方法。 "Invention 13"
The aluminum-based composite hydrophilic member according to invention 11 or invention 12, wherein in the second step, the hydrophilic fine particles are supported so that the mass of the hydrophilic fine particles is within a range of 0.1 g / m 2 to 20 g / m 2. Manufacturing method.
「発明１４」　
発明１１乃至発明１３のいずれか１つに記載の製造方法により製造したアルミニウム系複合親水性部材。 "Invention 14"
An aluminum-based composite hydrophilic member produced by the production method according to any one of Inventions 11 to 13.
次いで、本発明者等は、かかる課題を解決するため、鋭意検討を行ったところ、「水酸化リチウムを含む塩基性混合溶液」に「親水性微粒子」を混合してなる溶液または懸濁液を用いてアルミニウム系材料を接触処理することにより、網目状多孔質構造体が形成される側から親水性微粒子が速やかに担持され、簡単なプロセスにより親水性微粒子がより強固に担持された密着性に優れる親水性部材が得られることを見出し、本発明に到達した。　 Next, the present inventors conducted extensive studies to solve the above problems, and found that a solution or suspension obtained by mixing “hydrophilic fine particles” with “basic mixed solution containing lithium hydroxide” was obtained. By using the aluminum-based material for contact treatment, hydrophilic fine particles are quickly supported from the side on which the network porous structure is formed, and the hydrophilic fine particles are more firmly supported by a simple process. The present inventors have found that an excellent hydrophilic member can be obtained and have reached the present invention. *
なお、コロイダル金属酸化物やフィロ珪酸塩等の親水性微粒子は、アルカリ金属の水酸化物と反応することは当業者にも知られており、反応により形態の違う塩を形成する可能性もあり、親水性微粒子を、水酸化リチウムを含む塩基性混合溶液に混合懸濁させることは通常は行われないプロセスである。 In addition, it is known to those skilled in the art that hydrophilic fine particles such as colloidal metal oxides and phyllosilicates react with alkali metal hydroxides, and there is a possibility of forming different forms of salts depending on the reaction. Mixing and suspending hydrophilic fine particles in a basic mixed solution containing lithium hydroxide is a process that is not normally performed.
即ち、本発明において、アルミニウムもしくはその合金を、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液に親水性微粒子を混合してなる溶液または懸濁液で接触処理することにより、アルミニウムもしくはその合金の表層部の少なくとも一部に網目状多孔質構造体を担体として形成するとともに、当該担体に前記親水性微粒子を担持固定させたアルミニウム系親水性材料が製造できる。 That is, in the present invention, aluminum or an alloy thereof is contact-treated with a solution or suspension obtained by mixing hydrophilic fine particles in a basic mixed solution obtained by mixing a base containing lithium hydroxide, water, and an organic solvent. Thus, an aluminum-based hydrophilic material in which a network-like porous structure is formed as a carrier on at least a part of the surface layer portion of aluminum or an alloy thereof and the hydrophilic fine particles are supported and fixed on the carrier can be produced.
　即ち、本発明は、以下の発明１５～発明２１を含む。 That is, the present invention includes the following inventions 15 to 21.
「発明１５」　
アルミニウムもしくはその合金を、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液に親水性微粒子を混合してなる溶液または懸濁液で接触処理することにより、アルミニウムもしくはその合金の表層部の少なくとも一部に網目状多孔質構造体を形成するとともに、当該網目状多孔質構造体に前記親水性微粒子を担持固定させることを特徴とするアルミニウム系親水性部材。 "Invention 15"
By subjecting aluminum or an alloy thereof to contact treatment with a solution or suspension obtained by mixing hydrophilic fine particles in a basic mixed solution obtained by mixing a base containing lithium hydroxide, water and an organic solvent, aluminum or an alloy thereof is obtained. An aluminum-based hydrophilic member, characterized in that a network-like porous structure is formed on at least a part of the surface layer portion, and the hydrophilic fine particles are supported and fixed on the network-like porous structure.
「発明１６」　
塩基性混合溶液を構成する混合溶媒の表面張力が、１８ｍＮ／ｍ～６０ｍＮ／ｍの範囲内にあることを特徴とする発明１５に記載のアルミニウム系親水性部材。 "Invention 16"
16. The aluminum-based hydrophilic member according to invention 15, wherein the surface tension of the mixed solvent constituting the basic mixed solution is in the range of 18 mN / m to 60 mN / m.
「発明１７」　
塩基性混合溶液中の有機溶媒が、アルコール系、ニトリル系、ケトン系、エステル系、エーテル系、スルホキシド系、アミド系、グリコール系、芳香族系もしくは、含フッ素アルコール系の溶媒の少なくとも一種である発明１５または発明１６に記載のアルミニウム系親水性部材。 "Invention 17"
The organic solvent in the basic mixed solution is at least one of an alcohol, nitrile, ketone, ester, ether, sulfoxide, amide, glycol, aromatic, or fluorinated alcohol solvent. The aluminum-based hydrophilic member according to Invention 15 or Invention 16.
「発明１８」　
塩基性混合溶液のｐＨが、９．０～１３．５の範囲内にあることを特徴とする発明１５乃至発明１７のいずれか１つに記載のアルミニウム系親水性部材。 "Invention 18"
The aluminum-based hydrophilic member according to any one of Inventions 15 to 17, wherein the pH of the basic mixed solution is in the range of 9.0 to 13.5.
「発明１９」　
網目状多孔質構造体が孔径５ｎｍ～５００ｎｍ、深さ０．０５μｍ～１０μｍの範囲内の細孔を含むことを特徴とする発明１５に記載のアルミニウム系親水性部材。 "Invention 19"
The aluminum-based hydrophilic member according to invention 15, wherein the network porous structure includes pores having a pore diameter of 5 nm to 500 nm and a depth of 0.05 μm to 10 μm.
「発明２０」　
親水性微粒子がコロイダルシリカ、コロイダルアルミナ、コロイダルチタン、コロイダルスズ、コロイダルアンチモン、コロイダルムライト、コロイダル鉄、アルミナ、ゼオライト、シリカゲル、シリカ、アルミナ、チタニア、炭酸カルシウム、酸化カルシウム、タルク、珪藻土、バーミキュライト、ヒル石、弁柄、貝殻焼成カルシウムの微粒子、または、金、銀、白金、パラジウム、ルテニウム、銅、ニッケル、バナジウム、チタン、インジウム、スズ、タングステンのナノ金属粒子もしくはナノ金属コロイドよりなる群より選ばれる少なくとも一つである発明１５に記載のアルミニウム系親水性部材。 "Invention 20"
Hydrophilic fine particles are colloidal silica, colloidal alumina, colloidal titanium, colloidal tin, colloidal antimony, colloidal mullite, colloidal iron, alumina, zeolite, silica gel, silica, alumina, titania, calcium carbonate, calcium oxide, talc, diatomaceous earth, vermiculite, leech Selected from the group consisting of fine particles of stone, petals, shell calcined calcium, or nanometal particles or colloidal metal of gold, silver, platinum, palladium, ruthenium, copper, nickel, vanadium, titanium, indium, tin, tungsten The aluminum-based hydrophilic member according to invention 15, which is at least one.
「発明２１」　
親水性微粒子の質量が０．１ｇ／ｍ2～２０ｇ／ｍ2の範囲内になるように担持させることを特徴とする発明１５に記載のアルミニウム系親水性部材。 "Invention 21"
The aluminum-based hydrophilic member according to invention 15, wherein the hydrophilic fine particles are supported so that the mass of the hydrophilic fine particles is within a range of 0.1 g / m 2 to 20 g / m 2 .
実施例１において得られた網目状多孔質構造を有するアルミニウム板のＳＥＭ写真である。2 is a SEM photograph of an aluminum plate having a network porous structure obtained in Example 1. 実施例４において得られた網目状多孔質構造を有するアルミニウム不織布のＳＥＭ写真である。4 is a SEM photograph of an aluminum nonwoven fabric having a network porous structure obtained in Example 4. 実施例５において得られた網目状多孔質にゼオライト粒子を担持したアルミニウム不織布のＳＥＭ写真である。6 is an SEM photograph of an aluminum nonwoven fabric in which zeolite particles are supported on a mesh-like porous material obtained in Example 5. 比較例２で得られた（水酸化ナトリウム／水／エタノール）混合溶液で接触処理したアルミニウム板のＳＥＭ写真である。（網目状微細多孔質構造は観察されなかった。）4 is an SEM photograph of an aluminum plate contact-treated with a (sodium hydroxide / water / ethanol) mixed solution obtained in Comparative Example 2. FIG. (No reticulated microporous structure was observed.) 実施例１０において得られた網目状多孔質にＩＰＡ－ＳＴ微粒子を担持したアルミニウム板のＳＥＭ写真である。4 is an SEM photograph of an aluminum plate in which IPA-ST fine particles are supported on a mesh-like porous material obtained in Example 10. 実施例１５において得られた網目状多孔質にカオリナイト微粒子を担持したアルミニウム板のＳＥＭ写真である。6 is a SEM photograph of an aluminum plate having kaolinite fine particles supported on a mesh-like porous material obtained in Example 15.
詳細な説明Detailed description
本発明の網目状多孔質体は、その多孔質が担体として有用であることより、その多孔質の中に、触媒、色素、吸着性、親水性、撥水性の機能性を有する微粒子を担持固定化することにより当該機能を有する機能性材料として有用である。本発明の製造方法により、水酸化リチウムを含む塩基と水と有機溶媒を混合した混合塩基溶液でアルミニウム系材料を処理するという簡便な方法で当該網目状多孔質体を容易に製造できる。 Since the porous porous body of the present invention is useful as a carrier, fine particles having catalyst, dye, adsorptive, hydrophilic, and water-repellent functionalities are supported and fixed in the porous body. Therefore, it is useful as a functional material having this function. According to the production method of the present invention, the network porous body can be easily produced by a simple method of treating an aluminum-based material with a mixed base solution in which a base containing lithium hydroxide, water and an organic solvent are mixed.
　また、本発明のアルミニウム系親水性部材は、比較的簡便な方法により網目状多孔質構造に親水性粒子が担持された部材が得られるので工業的に有用である。本発明の親水性部材は、網目状多孔質構造体が形成される側から親水性微粒子が速やかに担持されるので、プロセス的に製造が簡単で、且つ密着性に優れた親水性部材が得られる。当該親水性部材は超親水性をしめすことより、ヒートパイプ、フィン等の熱交換素子の部材として有用である。 The aluminum-based hydrophilic member of the present invention is industrially useful because a member in which hydrophilic particles are supported on a mesh-like porous structure can be obtained by a relatively simple method. In the hydrophilic member of the present invention, hydrophilic fine particles are rapidly supported from the side on which the mesh-like porous structure is formed, so that a hydrophilic member that is easy to manufacture and has excellent adhesion can be obtained. It is done. The hydrophilic member is useful as a member of a heat exchange element such as a heat pipe or a fin because it exhibits super hydrophilicity.
即ち、本発明は、以下のとおりである。 That is, the present invention is as follows.
本発明者らは、上記問題を解決するために、アルミニウム系材料に化学的な処理を施し、細孔を形成させることを目的として一連の研究を重ねる過程で、アルミニウム系材料を、水酸化リチウムを含む塩基と水と有機溶媒を混合した塩基性混合溶液（特に特定の表面張力を有する塩基性混合溶液）で接触処理することにより、アルミニウム系材料の表面との濡れ性が改善され、アルミニウム表面と水酸化リチウムの速やかな反応が進行して、表層部の少なくとも一部に酸化被膜とは異なる網目状多孔質構造体が形成されることを見出し本発明に到達した。 In order to solve the above-mentioned problems, the inventors of the present invention have made a series of studies for the purpose of chemically treating an aluminum-based material and forming pores. Contact treatment with a basic mixed solution (especially a basic mixed solution having a specific surface tension) in which water and an organic solvent are mixed to improve the wettability with the surface of the aluminum-based material. As a result, the inventors have found that a network-like porous structure different from the oxide film is formed on at least a part of the surface layer portion by the rapid reaction between lithium hydroxide and lithium hydroxide.
最初に、本発明の網目状多孔質構造体およびその製造方法について詳しく説明する。 First, the network porous structure of the present invention and the production method thereof will be described in detail.
本発明の網目状多孔質構造体は、アルミニウム系材料を対象とし、その表面の少なくとも一部に網目状微細多孔質の細孔を生成させたものである。本発明の対象となるアルミニウム系材料は、純度９９．９質量％以上の純アルミニウムおよび各種のアルミニウム合金である。上記アルミニウム合金としては、具体的には、Ａ１０５０、Ａ１０７０、Ａ１０８０、Ａ１１００、Ａ１２００等のような微量のＳｉ、Ｆｅ、Ｃｕ、Ｍｎ、Ｍｇ等を含む合金、Ａ２０１４、Ａ２０１７、Ａ２０２４等のような特にＣｕを多く含む合金、Ａ５０５２、Ａ５０８３、Ａ５１５４のような特にＭｇを多く含む合金、Ａ７０７５、Ａ７Ｎ０１等のような特にＺｎを多く含む合金、ＡＤＣ１２等のような多量のＳｉを含む鋳物用合金等、各種の合金があげられる。上記アルミニウム等は、その形状等を問わない。また、アルミニウム系材料として、アルミニウム箔、インゴット、プレート、パイプ、アルミニウム繊維、ダイキャストこれらのアルミニウム等からなる中間製品、アルミニウム等からなる完成品の全てが本発明のアルミニウム等の範疇に含まれる。 The network-like porous structure of the present invention targets an aluminum-based material, and has network-like microporous pores formed on at least a part of its surface. The aluminum-based material that is the subject of the present invention is pure aluminum having a purity of 99.9% by mass or more and various aluminum alloys. Specific examples of the aluminum alloy include alloys containing trace amounts of Si, Fe, Cu, Mn, Mg, etc., such as A1050, A1070, A1080, A1100, A1200, etc., and particularly, A2014, A2017, A2024, etc. Alloys rich in Cu, alloys particularly rich in Mg such as A5052, A5083, A5154, alloys particularly rich in Zn such as A7075, A7N01, etc., casting alloys containing a large amount of Si such as ADC12, etc. There are various alloys. The said aluminum etc. do not ask | require the shape. In addition, as the aluminum-based material, aluminum foil, ingot, plate, pipe, aluminum fiber, die cast, intermediate products made of these aluminums, and finished products made of aluminum are all included in the category of aluminum of the present invention.
本発明のアルミニウム系網目状多孔質構造体は、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液でアルミニウム系材料を接触処理し、アルミニウム系材料の表面の少なくとも一部に網目状多孔質構造体を形成させることにより製造できる。 The aluminum-based network porous structure of the present invention is obtained by subjecting an aluminum-based material to contact treatment with a basic mixed solution obtained by mixing a base containing lithium hydroxide, water, and an organic solvent, and at least a part of the surface of the aluminum-based material. Can be produced by forming a mesh-like porous structure.
ここで、本発明でいう「溶液」とは溶質が溶媒に完全に溶解していることをいい、溶質が溶媒に分散しているものや懸濁しているものは含まない。また、当該溶媒が水と有機溶媒の混合溶媒である場合、混合溶媒は分離することなく均一であるものとする。 Here, the “solution” in the present invention means that the solute is completely dissolved in the solvent, and does not include those in which the solute is dispersed or suspended in the solvent. Moreover, when the said solvent is a mixed solvent of water and an organic solvent, a mixed solvent shall be uniform, without isolate | separating.
少なくとも水酸化リチウムと水と有機溶媒を混合した塩基性混合溶液の調製において、水酸化リチウム等の塩基は溶質に完全に溶解していることが必須である。当該塩基性混合溶液中の溶媒は、水と有機溶媒との混合溶媒であるが、当該有機溶媒としては通常は後述する親水性溶媒が用いられる。 In preparing a basic mixed solution in which at least lithium hydroxide, water and an organic solvent are mixed, it is essential that a base such as lithium hydroxide is completely dissolved in the solute. The solvent in the basic mixed solution is a mixed solvent of water and an organic solvent, and a hydrophilic solvent described later is usually used as the organic solvent.
混合溶媒の表面張力を調整することにより、後述のようにアルミニウム系材料の表面との濡れ性が改善される為、アルミニウム表面と水酸化リチウムの反応が速やかに進行する。かかる表面張力は、１８ｍＮ／ｍ～６０ｍＮ／ｍの範囲内にあり、２０ｍＮ／ｍ～５５ｍＮ／ｍが好ましく、２０ｍＮ／ｍ～５０ｍＮ／ｍがより好ましい。水の表面張力が２０℃において７２ｍＮ／ｍ程度であるが、有機溶媒を添加することにより表面張力を小さくすることができる。１８ｍＮ／ｍよりも小さい場合は、アルミニウム表面への濡れ性は優れるものの、水の含有量が極めて小さくなり水酸化リチウムが溶解しないため好ましくない。また、表面張力が５０ｍＮ／ｍよりも大きくなる場合は、アルミニウム表面への濡れ性が悪くなるため好ましくない。 By adjusting the surface tension of the mixed solvent, the wettability with the surface of the aluminum-based material is improved as will be described later, so that the reaction between the aluminum surface and lithium hydroxide proceeds promptly. Such surface tension is in the range of 18 mN / m to 60 mN / m, preferably 20 mN / m to 55 mN / m, and more preferably 20 mN / m to 50 mN / m. The surface tension of water is about 72 mN / m at 20 ° C., but the surface tension can be reduced by adding an organic solvent. If it is less than 18 mN / m, the wettability to the aluminum surface is excellent, but the water content becomes extremely small and lithium hydroxide does not dissolve, which is not preferable. Moreover, when surface tension becomes larger than 50 mN / m, since the wettability to the aluminum surface worsens, it is not preferable.
塩基性混合溶液を構成する混合溶媒において、上記の表面張力を与える範囲に入っていれば特に問題はないが、実質的に混合溶媒を調製するための目安として、有機溶媒と水との混合比は、容量比で、有機溶剤／水：９０／１０～１０／９０が好ましく、なかでも７０／３０～３０／７０が特に好ましい。 In the mixed solvent constituting the basic mixed solution, there is no particular problem as long as it is within the range giving the above surface tension, but as a guideline for substantially preparing the mixed solvent, the mixing ratio of the organic solvent and water Is preferably an organic solvent / water ratio of 90/10 to 10/90, and particularly preferably 70/30 to 30/70.
上記塩基性混合溶液は、（１）溶質が溶媒に溶解していること、および、（２）塩基性混合溶液を構成する混合溶媒の表面張力が上記範囲に入っているならば、調製方法は特に限定されないが、通常、水酸化リチウムを含む溶液を調製後、有機溶媒を添加して調製する方法が用いられる。塩基性混合溶液の場合と同様、水酸化リチウムを含む塩基性溶液は、水酸化リチウム等の溶質を溶解している必要があり、溶媒は「水単独」か「水と親水性有機溶媒との混合溶媒」にするのが良い。 If the basic mixed solution is (1) the solute is dissolved in the solvent, and (2) the surface tension of the mixed solvent constituting the basic mixed solution is within the above range, the preparation method is Although it does not specifically limit, Usually, after preparing the solution containing lithium hydroxide, the method of adding and preparing an organic solvent is used. As in the case of the basic mixed solution, the basic solution containing lithium hydroxide needs to dissolve a solute such as lithium hydroxide, and the solvent is “water alone” or “water and a hydrophilic organic solvent. It is preferable to use a “mixed solvent”.
　即ち、塩基性混合溶液の調整方法としては、
　「１」水酸化リチウム等の溶質を水に溶解させて塩基性溶液を調製後、次いで親水性有機溶媒を添加して調製する方法
　「２」水酸化リチウム等の溶質に「水と親水性有機溶媒の混合溶媒」を添加して溶解させ塩基性溶液を調製後、次いで同一または他の有機溶媒を添加する方法が挙げられるが、通常は「１」の方法が好適に用いられる。 That is, as a preparation method of the basic mixed solution,
“1” A method for preparing a basic solution by dissolving a solute such as lithium hydroxide in water, and then adding a hydrophilic organic solvent. “2” A solute such as lithium hydroxide containing “water and hydrophilic organic”. Examples of the method include adding a solvent mixed solvent and dissolving it to prepare a basic solution, and then adding the same or another organic solvent, but the method of “1” is usually preferably used.
前記親水性溶媒としては、炭素数１～７のアルコール系、ニトリル系、ケトン系、エーテル系、スルホキシド、アミド系、エステル系、グリコール系の溶媒が好適に用いられる。かかる溶媒としては、例えばメタノール、エタノール、イソプロパノール、アセトニトリル、プロピロニトリル、アセトン、メチルエチルケトン、ジメチルケトン、メチルイソブチルケトン、ジメチルエーテル、ジエチルエーテル、ジオキサン、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、蟻酸メチル、蟻酸エチル、酢酸メチル、酢酸エチル、酢酸ｎ－プロピル、酢酸ｉ－プロピル、エチレングリコール、プロピレングリコール等があげられるがこれらに限定されない。上記の親水性溶媒のなかでも、入手の関係でメタノール、エタノールが特に好ましい。なお、これらの溶媒は１種又は２種以上を混合して用いることができる。 As the hydrophilic solvent, alcohol-based, nitrile-based, ketone-based, ether-based, sulfoxide, amide-based, ester-based and glycol-based solvents having 1 to 7 carbon atoms are preferably used. Examples of the solvent include methanol, ethanol, isopropanol, acetonitrile, propyronitrile, acetone, methyl ethyl ketone, dimethyl ketone, methyl isobutyl ketone, dimethyl ether, diethyl ether, dioxane, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, dimethyl sulfoxide, dimethyl Examples include, but are not limited to, formamide, dimethylacetamide, methyl formate, ethyl formate, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, ethylene glycol, propylene glycol and the like. Among the above hydrophilic solvents, methanol and ethanol are particularly preferable because of availability. In addition, these solvents can be used 1 type or in mixture of 2 or more types.
次いで、上記塩基性溶液にさらに有機溶媒を混合して塩基性混合溶液の調製を行うが、塩基性溶液と有機溶剤との混合によって、水酸化リチウム等の溶質が析出しないことが重要である。塩基性溶液の溶媒が水単独であった場合は、使用する有機溶媒は、上記親水性溶媒が好適に用いられる。 Next, an organic solvent is further mixed with the basic solution to prepare a basic mixed solution. However, it is important that a solute such as lithium hydroxide does not precipitate due to the mixing of the basic solution and the organic solvent. When the solvent of the basic solution is water alone, the hydrophilic solvent is preferably used as the organic solvent to be used.
上記塩基性溶液の溶媒が、「水と親水性有機溶媒との混合溶媒」であった場合、有機溶媒として、上記の親水性有機溶媒中からさらに同種あるいは別の親水性有機溶媒を添加しても良いが、アルミニウム系材料表面へのさらなる濡れ性の改善を目的として、芳香族系、含フッ素アルコール系の溶剤を用いることができる。かかる溶剤としては、ベンゼン、トルエン、キシレン、ヘキサフルオロイソプロピルアルコール等が挙げられるが、これらに限定されない。なお、これらの溶剤は１種又は２種以上を混合して用いることができる。 When the solvent of the basic solution is “a mixed solvent of water and a hydrophilic organic solvent”, the same kind or another hydrophilic organic solvent is further added as an organic solvent from the above hydrophilic organic solvents. However, for the purpose of further improving wettability to the surface of the aluminum material, an aromatic solvent or a fluorinated alcohol solvent can be used. Such solvents include, but are not limited to, benzene, toluene, xylene, hexafluoroisopropyl alcohol, and the like. In addition, these solvents can be used 1 type or in mixture of 2 or more types.
適切な反応をさせるためには、塩基性混合溶液のｐＨは、ｐＨ９．０～ｐＨ１３．５の範囲内にあることが望ましい。ｐＨ９．０未満では反応が進行せず、ｐＨが１３．５を超えると被膜が激しく侵食されたり、網目状多孔質構造が破壊されて好ましくない。 In order to carry out an appropriate reaction, the pH of the basic mixed solution is desirably in the range of pH 9.0 to pH 13.5. If the pH is less than 9.0, the reaction does not proceed. If the pH exceeds 13.5, the coating is eroded violently or the network porous structure is destroyed, which is not preferable.
　上記混合溶液において、かかるｐＨを与える溶質の濃度は、塩基性混合液を構成する混合溶媒に対する水酸化リチウム等の塩基の溶解度の違いに依存するので一概には規定できないが、０．５質量％～５質量％が好ましく１．０質量％～３．５質量％とするのが特に好ましい。０．５質量％未満では、反応不足となり、反対に５質量％を超えると被膜が激しく侵食されたり、網目状多孔質構造が破壊されることがあり、好ましくない。 In the above mixed solution, the concentration of the solute that gives such pH depends on the difference in the solubility of the base such as lithium hydroxide in the mixed solvent constituting the basic mixed solution, and thus cannot be specified unconditionally. Is preferably 5% by mass, and more preferably 1.0% by mass to 3.5% by mass. If the amount is less than 0.5% by mass, the reaction is insufficient. On the other hand, if the amount exceeds 5% by mass, the coating is vigorously eroded or the network porous structure is destroyed, which is not preferable.
混合溶液が有機溶剤を全く含まない水溶液（表面張力　約７２ｍＮ／ｍ）である場合は、アルミニウム系材料の表面が撥水性であるために濡れ性が悪くなり、場合によっては塩基性溶液をはじいてしまうため均一な反応が進行しにくくなり好ましくない。また、塩基性水溶液の場合は、アルミニウム系材料との反応が進みにくいという欠点があり、反応が進行するまで数十分の誘導時間を要する。これはアルミニウムの表面に存在する数ｎｍの酸化アルミニウム被膜が不動態として働くためと考えられる。 When the mixed solution is an aqueous solution containing no organic solvent (surface tension: about 72 mN / m), the surface of the aluminum-based material is water-repellent, so that the wettability is deteriorated. In some cases, the basic solution is repelled. Therefore, a uniform reaction is difficult to proceed, which is not preferable. Moreover, in the case of a basic aqueous solution, there exists a fault that reaction with an aluminum-type material does not advance easily, and several tens of induction time is required until reaction advances. This is probably because an aluminum oxide film of several nm existing on the surface of aluminum works as a passive state.
アルミニウム系材料の表面の撥水性部分（酸化アルミニウム被膜）を除去するには、一般には脱脂洗浄や、サンドペーパー掛け、サンドブラスト掛け、アーク照射、プラズマ処理等の表面活性処理を行うが、表面活性処理時のムラにより均一に処理されない場合がある。本発明の製造方法では、有機溶媒を用いて混合溶液の表面張力を１８ｍＮ／ｍ～６０ｍＮ／ｍの範囲内に調整することにより、アルミニウム表面との濡れ性が改善されるため、表面処理時のムラに関係なく均一に反応させることが可能である。さらに、速やかに反応が進行するため、３０秒～１０分でアルミニウム材料の表面に均一な網目状多孔質構造を形成したアルミニウム系親水性部材が製造できる。 In order to remove the water-repellent part (aluminum oxide film) on the surface of the aluminum-based material, surface activation treatment such as degreasing cleaning, sandpaper application, sandblasting, arc irradiation, plasma treatment, etc. is generally performed. There may be cases where uniform processing is not possible due to unevenness in time. In the production method of the present invention, the wettability with the aluminum surface is improved by adjusting the surface tension of the mixed solution within the range of 18 mN / m to 60 mN / m using an organic solvent. It is possible to react uniformly regardless of unevenness. Furthermore, since the reaction proceeds promptly, an aluminum-based hydrophilic member in which a uniform network porous structure is formed on the surface of the aluminum material can be produced in 30 seconds to 10 minutes.
上記のように、第一工程の処理前にアルミニウム材料の脱脂洗浄や表面活性処理を行ってもよいが、作業が煩雑となるため工業的な方法ではない。本発明の製造方法は、水酸化リチウムを含む塩基性混合溶液がある程度の脱脂力を有しているため、脱脂洗浄や表面活性処理を省略することができる優れた方法である。 As described above, degreasing and surface activation treatment of the aluminum material may be performed before the treatment in the first step, but this is not an industrial method because the operation becomes complicated. Since the basic mixed solution containing lithium hydroxide has a certain degree of degreasing power, the production method of the present invention is an excellent method that can omit degreasing and surface activation treatment.
上記混合溶液の調製において、ｐＨが９．０～１３．５の範囲をとる限りにおいては、溶質として水酸化リチウムの他にアルカリ金属水酸化物あるいはアルカリ土類金属水酸化物をさらに添加することができる。用いるアルカリ金属水酸化物としては、水酸化ナトリウム、水酸化リチウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム等の水酸化物があげられる。また、アルカリ土類金属水酸化物としては、水酸化ベリリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム等の水酸化物があげられる。 In the preparation of the mixed solution, as long as the pH is in the range of 9.0 to 13.5, an alkali metal hydroxide or an alkaline earth metal hydroxide is further added as a solute in addition to lithium hydroxide. Can do. Examples of the alkali metal hydroxide used include hydroxides such as sodium hydroxide, lithium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Examples of the alkaline earth metal hydroxide include hydroxides such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide.
アルカリ金属水酸化物およびアルカリ土類金属水酸化物によって、溶媒への溶解度、塩基の強さが異なるため、一概には規定できないが、混合溶液中に含まれる溶質である「水酸化リチウムと他のアルカリ金属水酸化物」もしくは「水酸化リチウムとアルカリ土類金属水酸化物」の濃度は、水酸化リチウムを最低限０．５質量％含み且つトータルで「０．５質量％より大きく５質量％以下」とするのが望ましい。この範囲内において、「水酸化リチウムと他のアルカリ金属水酸化物」、または「水酸化リチウムとアルカリ土類金属水酸化物」の混合割合を適宜調整することにより、ｐＨの範囲を９．０～１３．５に調製することができる。０．５質量％以下では、反応不足となり、反対に５質量％を超えると被膜が激しく侵食されまた微細孔が破壊されて好ましくない。特に、塩基性混合溶液の濃度は１．０質量％～３．５質量％にするのが好適である。 Since alkali metal hydroxides and alkaline earth metal hydroxides differ in solubility in solvents and base strength, they cannot be specified unconditionally. However, the solute contained in the mixed solution is “lithium hydroxide and others. The concentration of “alkaline metal hydroxide” or “lithium hydroxide and alkaline earth metal hydroxide” includes a minimum of 0.5% by mass of lithium hydroxide and a total of “greater than 0.5% by mass and 5% by mass. % Or less "is desirable. Within this range, the pH range is adjusted to 9.0 by appropriately adjusting the mixing ratio of “lithium hydroxide and other alkali metal hydroxide” or “lithium hydroxide and alkaline earth metal hydroxide”. To 13.5. If the amount is less than 0.5% by mass, the reaction is insufficient. On the other hand, if the amount exceeds 5% by mass, the coating is vigorously eroded and micropores are destroyed. In particular, the concentration of the basic mixed solution is preferably 1.0% by mass to 3.5% by mass.
他のアルカリ金属水酸化物もしくはアルカリ金属水酸化物をさらに添加して用いる場合の調製方法については、水酸化リチウム単独の場合に準じて行うことができる。 About the preparation method in the case of adding and using another alkali metal hydroxide or alkali metal hydroxide, it can carry out according to the case of lithium hydroxide alone.
本発明の網目状多孔質構造体の製造方法において、アルミニウム系材料を塩基性混合溶液で処理するにあたり、アルミニウム系材料を当該塩基性混合溶液と接触させる必要がある。接触させる方法は、特に限定されないが、当該塩基性混合溶液をスプレー等で吹き付ける方法、シリンジ等で滴下する方法、塩基性混合溶液の処理浴の中に浸漬する方法が挙げられるが、処理浴に浸漬する方法が好適に用いられる。処理浴への浸漬時間は、アルミニウム系材料の種類、形状、寸法、および塩基性水溶液の濃度、組成、浴温等に応じて適当な時間を選べばよく、通常は３０秒～１５分に設定される。また、浴温についても、浸漬時間との兼ね合いにより、適当な温度に設定すればよいが、通常は、塩基性溶液は、常温～５０℃程度に設定され、より好適には、２０℃～４０℃に設定される。上記温度範囲よりも低いと、反応の進行に要する時間が非常に長くなり、反対に高いと、反応が速くなりすぎて、被膜が激しく侵食されたり、網目状多孔質構造が破壊されたり、表面が不均一になりやすく好ましくない。 In the method for producing a reticulated porous structure of the present invention, when an aluminum-based material is treated with a basic mixed solution, the aluminum-based material needs to be brought into contact with the basic mixed solution. The method of contacting is not particularly limited, and examples thereof include a method of spraying the basic mixed solution with a spray, a method of dropping with a syringe or the like, and a method of immersing in a processing bath of the basic mixed solution. A dipping method is preferably used. The immersion time in the treatment bath may be selected appropriately depending on the type, shape, and dimensions of the aluminum-based material, the concentration of the basic aqueous solution, the composition, the bath temperature, etc., and is usually set to 30 seconds to 15 minutes. Is done. Further, the bath temperature may be set to an appropriate temperature in consideration of the immersion time. Usually, the basic solution is set to room temperature to about 50 ° C., more preferably 20 ° C. to 40 ° C. Set to ° C. When the temperature is lower than the above temperature range, the time required for the reaction to proceed is very long. On the other hand, when the temperature is high, the reaction becomes too fast, the coating is eroded violently, the mesh porous structure is destroyed, the surface Tends to be non-uniform.
アルミニウム材料を浸漬させると、アルミニウムと水酸化リチウムの反応が進行し、浸漬後３０秒～５分でアルミニウム材料表面から微細な水素発泡が観察される。目安として発泡してから３０秒～５分の時間浸漬させることにより適度な反応を行わせることができる。 When the aluminum material is immersed, the reaction between aluminum and lithium hydroxide proceeds, and fine hydrogen foaming is observed from the surface of the aluminum material 30 seconds to 5 minutes after immersion. As a guide, moderate reaction can be performed by dipping for 30 seconds to 5 minutes after foaming.
上記化学的処理において、処理浴中に浸漬した後に乾燥処理することが好ましい。乾燥処理は、通常は常温でもよいし、または熱風で加熱乾燥してもよい。また乾燥後にアルミニウムの基材をある程度の温度（１００℃～３５０℃程度）まで加熱することも可能であり、特に限定されることなく各種の方法が行われる。この乾燥または加熱乾燥により、溶媒である親水性有機溶剤と水の混合溶媒は徐々に表面から蒸発し、その過程において表面にアルカリ成分が残留して徐々に濃度が上昇してアルミニウムの表面から反応が進み、金属結晶の結晶粒子が溶出して粒界壁を残した網目状構造が形成されるものと考えられる。 In the above chemical treatment, it is preferable to perform a drying treatment after being immersed in a treatment bath. The drying treatment may be performed at normal temperature or may be heated and dried with hot air. It is also possible to heat the aluminum substrate to a certain temperature (about 100 ° C. to 350 ° C.) after drying, and various methods are performed without any particular limitation. By this drying or heat drying, the solvent mixture of hydrophilic organic solvent and water gradually evaporates from the surface, and in the process, alkali components remain on the surface and the concentration gradually increases and reacts from the aluminum surface. Thus, it is considered that a network structure is formed in which the crystal grains of metal crystals are eluted and leave the grain boundary walls.
　但し、温度勾配がある場合は表面での反応に偏りが生じるため好ましくない。また、乾燥処理を経ることなく水洗いした場合でも網目状構造体は形成されるので、乾燥処理は必須ではないものの、充分な網目構造を形成させる目的で、上記のような乾燥処理を入れることが望ましい。 However, if there is a temperature gradient, the reaction at the surface is biased, which is not preferable. In addition, a network structure is formed even when washed with water without passing through a drying process. Therefore, although the drying process is not essential, the above-described drying process may be performed for the purpose of forming a sufficient network structure. desirable.
本発明の方法で形成した網目状多孔質体の表面を、走査型電子顕微鏡（略称、ＳＥＭ）で観察したところ、孔径５ｎｍ～５００ｎｍ、深さ０．０５μｍ～１０μｍの範囲内の細孔が規則正しく並んでいることが観測された（実施例参照）。 When the surface of the mesh-like porous body formed by the method of the present invention was observed with a scanning electron microscope (abbreviation, SEM), pores within a pore diameter range of 5 nm to 500 nm and a depth of 0.05 μm to 10 μm were regularly formed. It was observed that they were lined up (see Examples).
当該網目状多孔質構造体は、その多孔質が担体として有用であり、その多孔質の中に、触媒、色素、吸着性、親水性、撥水性等の機能性を有する微粒子を担持固定化することにより機能性を発現させることが可能である。 The network porous structure is useful as a carrier, and supports and immobilizes fine particles having functions such as catalyst, dye, adsorptivity, hydrophilicity, and water repellency in the porous structure. It is possible to express functionality.
　微粒子の粒子径は、特に限定はされないが、５ｎｍ～５０μｍの範囲内にあることが好ましい。平均粒径が５ｎｍ未満であると、微粒子の粒径が小さ過ぎて長期の塗布時間が必要で効率が悪くまた、微粒子の有する表面エネルギーが非常に大きくなり、単分散が困難で凝集しやすく取り扱いが非常に困難である。一方、微粒子の平均粒径が５０μｍを越えると、被膜上の網目状多孔質構造体の孔径よりも遥かに大きくなるために重力の影響が大きくなり孔径中に取り込まれた微粒子が保持しきれなくなり、摩擦により容易に剥がれてしまう等の問題が発生する。より好ましくは０．０５μｍ～４０μｍ、さらに好ましくは０．５μｍ～２０μｍである。 The particle diameter of the fine particles is not particularly limited, but is preferably in the range of 5 nm to 50 μm. If the average particle size is less than 5 nm, the particle size of the fine particles is too small, requiring a long coating time, resulting in poor efficiency. Also, the surface energy of the fine particles becomes very large, making monodispersion difficult and easy to aggregate. Is very difficult. On the other hand, if the average particle size of the fine particles exceeds 50 μm, the influence of gravity increases because the particle size is much larger than the pore size of the mesh-like porous structure on the coating, and the fine particles incorporated in the pore size cannot be retained. The problem of peeling off easily due to friction occurs. More preferably, it is 0.05 μm to 40 μm, and still more preferably 0.5 μm to 20 μm.
　なお、ここでいう粒子の粒径は所謂１次粒子の大きさを示し、微粒子同士が凝集した２次粒子の大きさを示しているのではない。親水膜においては、２次粒子の大きさは成膜に困難がなければ、特に限定されるものではない。 Note that the particle size of the particles referred to here indicates the size of so-called primary particles, and does not indicate the size of secondary particles in which fine particles are aggregated. In the hydrophilic film, the size of the secondary particles is not particularly limited as long as there is no difficulty in film formation.
　前記の微粒子を網目状多孔質構造体に導入するにあたり、まず、微粒子の懸濁液を調製する。溶媒は微粒子の懸濁液を調製できるものであれば特に限定されないが、選択した微粒子の濡れ性等を勘案して適宜選択すればよい。具体的には、水、メタノール、エタノール、ｉ－プロパノール、ｎ－プロパノール、ｎ－ブタノール、ｉ－ブタノール、ｔ－ブタノール、メトキシエタノール、エトキシエタノール等のアルコール類、エチレングリコール、酢酸エステル、カルボン酸、低級炭化水素、脂肪族、芳香族等の一般溶剤、又はこれらの混合物よりなる混合物をよりなる溶媒を用いて微粒子が懸濁化された懸濁液を調製する。また、分散性を改良するために分散剤等を添加してもよい。 In introducing the fine particles into the network porous structure, first, a fine particle suspension is prepared. The solvent is not particularly limited as long as it can prepare a suspension of fine particles, but may be appropriately selected in consideration of wettability of the selected fine particles. Specifically, water, methanol, ethanol, i-propanol, n-propanol, n-butanol, i-butanol, t-butanol, alcohols such as methoxyethanol, ethoxyethanol, ethylene glycol, acetate ester, carboxylic acid, A suspension in which the fine particles are suspended is prepared using a solvent composed of a general solvent such as lower hydrocarbon, aliphatic, aromatic, or a mixture thereof. Moreover, you may add a dispersing agent etc. in order to improve a dispersibility.
　網目状多孔質構造体に当該微粒子を担持固定化する方法としては、微粒子を導入できるものであれば特に限定されず、上記懸濁液をコーティングする方法、または該懸濁液を含浸させる方法が挙げられる。 The method for supporting and immobilizing the fine particles on the network porous structure is not particularly limited as long as the fine particles can be introduced, and a method of coating the suspension or a method of impregnating the suspension may be used. Can be mentioned.
懸濁液をコーティングする方法としては、湿式ではディップコート、フローコート、スプレーコート、メッキ、無電界メッキ、スクリーン印刷、フレキソ印刷等の手段で行うことができ、ディップコート、スプレーコート、メッキ、無電界メッキが簡便な方法として好適に用いられる。 As a method of coating the suspension, wet coating can be performed by means of dip coating, flow coating, spray coating, plating, electroless plating, screen printing, flexographic printing, etc., and dip coating, spray coating, plating, no Electroplating is suitably used as a simple method.
　懸濁液のコーティングは乾式で行うこともでき、静電塗装法により帯電させた粉体を反対に帯電させた試料に衝突させて効率よく付着させる手法や、ブラスト法により親水性微粒子を高速で吹き付けて微細孔に緻密に塗布する手法が好適に用いられる。 Suspension coating can also be carried out dry, by applying a method in which the powder charged by the electrostatic coating method is made to collide with the oppositely charged sample for efficient adhesion, or the hydrophilic fine particles are applied at high speed by the blast method. A method of spraying and finely coating the fine holes is preferably used.
　懸濁液を含浸させる方法としては、常圧含浸法、減圧含浸法、加圧含浸法、ゾルゲル法、電気泳動法、浸漬超音波含浸法などがあり、常圧含浸法、減圧含浸法、加圧含浸法、浸漬超音波含親法が好適に用いられる。中でも、減圧加圧を併用する含浸法が好ましい。具体的な含浸法としては適当な真空容器中に網目状多孔質構造を形成したアルミニウム部材を置き、内部を減圧にしてから、当該微粒子の懸濁液を導入することによって表面細孔内に当該微粒子を密に充填することが出来る。また懸濁液を導入してから容器を加圧にしてより多くの微粒子を充填することもできる。また、浸漬超音波法も好適に用いられ、懸濁液に網目状多孔質構造を形成したアルミニウム部材を浸漬して、超音波をあてながら微粒子を導入するので、網目状多孔質構造の細部にまで微粒子が充填できる。 Methods for impregnating the suspension include atmospheric pressure impregnation method, reduced pressure impregnation method, pressure impregnation method, sol-gel method, electrophoresis method, immersion ultrasonic impregnation method, etc. A pressure impregnation method and an immersion ultrasonic parent method are preferably used. Among them, the impregnation method using pressure reduction and pressurization is preferable. As a specific impregnation method, an aluminum member having a network-like porous structure is placed in a suitable vacuum vessel, the pressure inside is reduced, and the suspension of the fine particles is introduced into the surface pores. The fine particles can be densely packed. It is also possible to fill the container with more fine particles by introducing the suspension and then pressurizing the container. In addition, the immersion ultrasonic method is also preferably used, and the fine particles are introduced while immersing the aluminum member in which the mesh-like porous structure is formed in the suspension and applying ultrasonic waves. Can be filled with fine particles.
　コーティングあるいは含浸により微粒子を導入後、乾燥・加熱することにより、造膜することができ、微粒子を担持固定することができる。乾燥・加熱処理方法は、特に限定されないが、常温で乾燥してもよいし、または熱風で加熱乾燥してもよい。また乾燥後にアルミニウムの基材を１００℃～３５０℃まで加熱してさらに乾燥する手法も用いられ、例えば、室温で３０分乾燥後、１５０℃のオーブンで１時間程度加熱する方法が用いられる。このようにして、アルミニウム系複合親水性部材が製造できる。 After introducing the fine particles by coating or impregnation, the film can be formed by drying and heating, and the fine particles can be supported and fixed. The drying / heating treatment method is not particularly limited, and may be dried at room temperature or may be heated and dried with hot air. Further, after drying, a method in which the aluminum base material is further heated to 100 ° C. to 350 ° C. and further dried is used. For example, after drying at room temperature for 30 minutes, a method of heating in an oven at 150 ° C. for about 1 hour is used. In this way, an aluminum based composite hydrophilic member can be produced.
　前記機能性を有する微粒子として、例えば吸着性を有する微粒子を担持することができ、１０ｎｍ～５００ｎｍ程度の粒径を持つゼオライト（例えば、ゼオラム）を用いて充填、担持固定した場合は、吸着性機能を付与したアルミニウム部材とすることができる。 As the fine particles having the functionality, for example, fine particles having an adsorptive property can be supported, and when adsorbing function is carried out by using a zeolite having a particle size of about 10 nm to 500 nm (for example, zeolite) filled and supported. It can be set as the aluminum member which provided.
　触媒機能を有する微粒子として、例えば光触媒を担持することができ、酸化チタン（例えば、石原産業株式会社製、商品名、ＳＴシリーズ）を用いて充填、担持固定した場合は、光触媒機能を付与したアルミニウム部材とすることができる。 As fine particles having a catalytic function, for example, a photocatalyst can be supported, and when filled and supported using titanium oxide (for example, trade name, ST series, manufactured by Ishihara Sangyo Co., Ltd.), aluminum provided with a photocatalytic function It can be a member.
　また、酸化触媒能を有する金属を導入した場合、有害ガス、揮発性有機化合物等を分解することが可能となり、環境浄化機能を有する部材とすることができる。かかる金属としては、パラジウム、白金、ルテニウム、ロジウム、イリジウム、ニッケル、コバルト、マンガン等が挙げられ、当該金属塩の溶液を用いた含浸法が好適に用いられる。 In addition, when a metal having an oxidation catalyst ability is introduced, it becomes possible to decompose harmful gases, volatile organic compounds, etc., and to make a member having an environmental purification function. Examples of such metals include palladium, platinum, ruthenium, rhodium, iridium, nickel, cobalt, manganese, and the like, and an impregnation method using a solution of the metal salt is preferably used.
例えば白金を導入する場合は、塩化白金酸の水溶液に本発明の網目状多孔質構造形成したアルミニウム部材を浸漬して、塩化白金酸の結晶を網目状多孔質膜に充填し、次いで空気中で焼成して白金の酸化物粒子した後に還元することにより、充填、担持固定化することが可能である。 For example, when introducing platinum, an aluminum member having a network porous structure according to the present invention is immersed in an aqueous solution of chloroplatinic acid to fill the network porous membrane with chloroplatinic acid crystals, and then in the air. Filling and supporting / immobilizing can be performed by reducing platinum oxide particles after firing.
上記のように本発明の網目状多孔質構造体は、微粒子を担持する担体として有用であり、機能性を有する微粒子を担持させることにより、容易に機能性を有するアルミニウム部材を製造できる。 As described above, the network porous structure of the present invention is useful as a carrier for supporting fine particles, and a functional aluminum member can be easily produced by supporting fine particles having functionality.
次いで、アルミニウム系材料を、水酸化リチウムを含む塩基と水と有機溶媒を混合した塩基性混合溶液（特に特定の表面張力を有する塩基性混合溶液）で処理することにより、アルミニウム系材料の表面との濡れ性が改善され、アルミニウム表面と水酸化リチウムの速やかな反応が進行して、表層部の少なくとも一部に酸化被膜とは異なる網目状多孔質構造体が形成され、親水性が著しく向上した親水性部材が得られることを見出し本発明に到達した。また、当該親水性部材に対してさらに親水性処理を施した親水性複合部材についても良好な親水性を維持することが認められた。 Next, the aluminum-based material is treated with a basic mixed solution (particularly a basic mixed solution having a specific surface tension) in which a base containing lithium hydroxide, water, and an organic solvent are mixed. Improved wettability, and the rapid reaction between the aluminum surface and lithium hydroxide progressed, and a network-like porous structure different from the oxide film was formed on at least a part of the surface layer, and the hydrophilicity was remarkably improved. The inventors have found that a hydrophilic member can be obtained and have reached the present invention. In addition, it was confirmed that the hydrophilic composite member obtained by further subjecting the hydrophilic member to hydrophilic treatment maintains good hydrophilicity.
アルミニウムもしくはその合金（以下、統合してアルミニウム系ということもある）の表面に形成させた網目状多孔質構造体よりなる親水性部材および当該親水性部材にさらなる親水性処理を施した複合親水性部材、さらにはそれらの製造方法について説明する。 A hydrophilic member made of a network-like porous structure formed on the surface of aluminum or an alloy thereof (hereinafter sometimes referred to as an aluminum group), and a composite hydrophilic property obtained by subjecting the hydrophilic member to further hydrophilic treatment The members and the manufacturing method thereof will be described.
アルミニウム系親水性部材は、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液で母材であるアルミニウム系材料を処理し、アルミニウム系材料の表面の少なくとも一部に網目状多孔質構造体を形成させる前述の網目状多孔質構造体およびその製造方法（第一工程）により製造できる。当該親水性部材は、それ自体でも優れた親水性を発現するが、第一工程で得られたアルミニウム系親水部材の網目状微小多孔質構造を担体として利用してさらなる親水性処理（第二工程）を施すことにより、機能性を有したアルミニウム系複合親水性部材が製造できる。 An aluminum-based hydrophilic member treats an aluminum-based material as a base material with a basic mixed solution in which a base containing lithium hydroxide, water, and an organic solvent are mixed, and at least part of the surface of the aluminum-based material has a mesh shape. It can be produced by the above-mentioned network-like porous structure for forming the porous structure and the production method (first step). Although the hydrophilic member itself exhibits excellent hydrophilicity, further hydrophilic treatment (second step) using the network-like microporous structure of the aluminum-based hydrophilic member obtained in the first step as a carrier. ), An aluminum based composite hydrophilic member having functionality can be manufactured.
　アルミニウム系材料は前述のものが好適に使用される。 The aforementioned aluminum materials are preferably used.
尚、アルミニウム系材料の中でも、メッシュ状のものは表面積が大きいため、熱交換素子等のフィン、低温加湿装置の親水膜等の用途に好適に用いられる。メッシュ状のアルミニウム系材料は、アルミニウム金属不織布として入手できる。アルミニウム金属不織布シートは、アルミニウム金属繊維を板状に堆積してなるアルミニウム金属綿板を焼結処理したものを圧延して形成されたもので、アルミニウム繊維相互間に複雑に折れ曲がっているので、表面積が大きいという特徴がある。 Of the aluminum-based materials, the mesh-shaped material has a large surface area, and thus is suitably used for applications such as fins for heat exchange elements, hydrophilic films for low-temperature humidifiers, and the like. The mesh-like aluminum-based material can be obtained as an aluminum metal nonwoven fabric. The aluminum metal nonwoven fabric sheet is formed by rolling a sintered aluminum metal cotton sheet obtained by depositing aluminum metal fibers in a plate shape, and is complicatedly folded between the aluminum fibers. There is a feature that is large.
第１工程は、前述の網目状多孔質構造体およびその製造方法と同様である。 The first step is the same as the above-described network-like porous structure and its manufacturing method.
本発明のアルミニウム系親水性部材は、下記、第一工程より製造できる。
第一工程：アルミニウムもしくはその合金を、少なくとも水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液で処理することにより、アルミニウムもしくはその合金の表層部の少なくとも一部に、網目状多孔質の細孔を形成する工程。 The aluminum-based hydrophilic member of the present invention can be produced from the following first step.
First step: By treating aluminum or an alloy thereof with a basic mixed solution in which a base containing at least lithium hydroxide, water, and an organic solvent are mixed, at least a part of the surface layer portion of aluminum or the alloy is formed into a mesh. Forming a fine porous pore.
尚、混合溶媒には前述の溶媒を混合したものを用いて、同じように調整した、同様の性質を持つ物を使用することが好ましい。 In addition, it is preferable to use the thing with the same property adjusted similarly using what mixed the above-mentioned solvent as a mixed solvent.
　本発明の第一工程の処理により得られるアルミニウム系親水性部材の表面を走査型電子顕微鏡で観察したところ、孔径５ｎｍ～５００ｎｍ、深さ０．０５μｍ～１０μｍの範囲内の細孔が網目状に規則正しく並んでいることが観測され、網目状多孔質構造を有することが判った。 When the surface of the aluminum-based hydrophilic member obtained by the treatment in the first step of the present invention was observed with a scanning electron microscope, the pores having a pore diameter of 5 nm to 500 nm and a depth of 0.05 μm to 10 μm were reticulated. It was observed that they were regularly arranged, and it was found to have a reticulated porous structure.
　本発明の親水性部材において、その純水接触角は３０度以下であることが望ましい。その純水接触角が３０度を超えると、所定の親水性が得られないからである。より好ましくは２０度以下、さらに好ましくは１０度以下である。ここで、純水接触角が３０度以下としたのは、例えば純水接触角が５度よりも小さくなると、高精度の測定は難しくなるが、極めて０度に近い純水接触角の親水性示す場合も含むからである。本明細書では、１０度以下の純粋接触角を示す場合、「超親水性」と評価する。なお、純水接触角の測定は、ＪＩＳ　Ｒ　３２５７：１９９９「基板ガラス表面の濡れ性試験方法」に準じて行われる。 In the hydrophilic member of the present invention, the pure water contact angle is desirably 30 degrees or less. This is because if the pure water contact angle exceeds 30 degrees, the predetermined hydrophilicity cannot be obtained. More preferably, it is 20 degrees or less, and more preferably 10 degrees or less. Here, the pure water contact angle is set to 30 degrees or less. For example, if the pure water contact angle is smaller than 5 degrees, high-precision measurement becomes difficult, but the hydrophilicity of the pure water contact angle is extremely close to 0 degrees. It is because the case where it shows is also included. In this specification, when a pure contact angle of 10 degrees or less is shown, it is evaluated as “superhydrophilic”. The pure water contact angle is measured according to JIS R 3257: 1999 “Test method for wettability of substrate glass surface”.
　上記、第一工程で得られた網目状多孔質構造を有するアルミニウム系部材の純水接触角を測定すると、水滴は被膜表面を広がり、接触角が測定できない程度に小さくなり、被膜が超親水性であることが観察できる。 When the pure water contact angle of the aluminum-based member having the network porous structure obtained in the first step is measured, the water droplet spreads on the surface of the coating and becomes so small that the contact angle cannot be measured, and the coating is super hydrophilic. Can be observed.
　次に、第二工程について説明する。第二工程は、第一工程で得られたアルミニウム系親水部材の網目状微小多孔質構造を担体として利用してさらなる親水処理を施すことにより、機能性を有したアルミニウム系複合親水性部材を製造する工程である。親水性処理を施すことにより表面に親水性が付与され、見かけの純水接触角はますます親水性が強くなるため、初期の微細な水滴が付着かつ成長しづらく、超親水性の機能を発現する親水被膜が得られる。 Next, the second process will be described. The second step produces a functional aluminum-based composite hydrophilic member by performing further hydrophilic treatment using the mesh-like microporous structure of the aluminum-based hydrophilic member obtained in the first step as a carrier. It is a process to do. By applying hydrophilic treatment, hydrophilicity is imparted to the surface, and the apparent pure water contact angle becomes more hydrophilic, making it difficult for initial fine water droplets to adhere and grow, and to express super hydrophilicity. A hydrophilic coating is obtained.
　本発明の第二工程の親水性処理は、第一工程で得られた網目状多孔質構造を有するアルミニウム系部材の多孔質部位を担体として、親水性を有する機能性微粒子を担持固定させることを目的とする。この工程により、アルミニウム系複合親水性部材を製造することが可能となる。 The hydrophilic treatment in the second step of the present invention is to carry and fix hydrophilic functional fine particles with the porous portion of the aluminum-based member having a network porous structure obtained in the first step as a carrier. Objective. This step makes it possible to produce an aluminum-based composite hydrophilic member.
　第一工程で得られたアルミニウム系親水性部材は、親水性の孔径５ｎｍ～５００ｎｍの網目状多孔質構造体である。当該多孔質構造体の孔径にフィットするような親水性の微粒子をアンカーとして導入することにより、共に親水性である微粒子と多孔質構造体が付着するため強固な密着性を有する。用いる無機微粒子の中には、５００ｎｍより大きい粒子径を有するものがあるが、アンカーとして孔内に入った無機微粒子の最表面の部分とそれよりも大きい無機微粒子間での強固な結合が形成されるため、孔内の微粒子が膜の外側の粒子を保持する形で、複雑な表面を形成し比表面積の大きい被膜で覆われるものと思われる。当該被膜は親水性微粒子で構成されるため、優れた親水性が発現し、アルミニウム系親水性複合部材として有用である。 The aluminum-based hydrophilic member obtained in the first step is a network-like porous structure having a hydrophilic pore diameter of 5 nm to 500 nm. By introducing hydrophilic fine particles that fit the pore size of the porous structure as anchors, the fine particles that are both hydrophilic and the porous structure adhere to each other, thereby having strong adhesion. Some of the inorganic fine particles used have a particle diameter larger than 500 nm, but a strong bond is formed between the outermost surface portion of the inorganic fine particles that have entered the hole as an anchor and the larger inorganic fine particles. Therefore, it is considered that the fine particles in the pores hold the particles outside the membrane, form a complex surface, and are covered with a coating having a large specific surface area. Since the coating is composed of hydrophilic fine particles, it exhibits excellent hydrophilicity and is useful as an aluminum-based hydrophilic composite member.
　微粒子の粒子径は、特に限定はされないが、５ｎｍ～５０μｍの範囲内にあることが好ましい。平均粒径が５ｎｍ未満であると、微粒子の粒径が小さ過ぎて長期の塗布時間が必要で効率が悪くまた、微粒子の有する表面エネルギーが非常に大きくなり、単分散が困難で凝集しやすく取り扱いが非常に困難である。一方、微粒子の平均粒径が５０μｍを越えると、被膜上の網目状多孔質構造体の孔径よりも遥かに大きくなるために重力の影響が大きくなり孔径中に取り込まれた微粒子が保持しきれなくなり、摩擦により容易に剥がれてしまう等の問題が発生する。より好ましくは０．０５μｍ～４０μｍ、さらに好ましくは０．５μｍ～２０μｍである。 The particle diameter of the fine particles is not particularly limited, but is preferably in the range of 5 nm to 50 μm. If the average particle size is less than 5 nm, the particle size of the fine particles is too small, requiring a long coating time, resulting in poor efficiency. Also, the surface energy of the fine particles becomes very large, making monodispersion difficult and easy to aggregate. Is very difficult. On the other hand, if the average particle size of the fine particles exceeds 50 μm, the influence of gravity increases because the particle size is much larger than the pore size of the mesh-like porous structure on the coating, and the fine particles incorporated in the pore size cannot be retained. The problem of peeling off easily due to friction occurs. More preferably, it is 0.05 μm to 40 μm, and still more preferably 0.5 μm to 20 μm.
　なお、ここでいう粒子の粒径は所謂１次粒子の大きさを示し、微粒子同士が凝集した２次粒子の大きさを示しているのではない。親水膜においては、２次粒子の大きさは成膜に困難がなければ、特に限定されるものではない。 Note that the particle size of the particles referred to here indicates the size of so-called primary particles, and does not indicate the size of secondary particles in which fine particles are aggregated. In the hydrophilic film, the size of the secondary particles is not particularly limited as long as there is no difficulty in film formation.
　第２工程の親水性処理工程において、担持される親水性微粒子の単位面積当たりの質量は０．１ｇ／ｍ2～２０ｇ／ｍ2の範囲内にあることが必要である。この親水性微粒子の単位面積当たりの質量が０．１ｇ／ｍ2未満の場合には充分な被覆がなされず、被覆にムラが生じるため好ましくない。一方、親水性微粒子の質量が２０ｇ／ｍ2を超える場合には、網目状多孔質が微粉末で全面にわたって被覆され、完全に網目状多孔質が埋没して表面積が低下するため親水性が劣るばかりか経済的ではなく、摩擦や振動で容易に剥離脱落して機械的強度に著しく支障をきたす。 In the hydrophilic treatment step of the second step, the mass per unit area of the supported hydrophilic fine particles needs to be within the range of 0.1 g / m 2 to 20 g / m 2 . If the mass per unit area of the hydrophilic fine particles is less than 0.1 g / m 2 , it is not preferable because sufficient coating is not performed and unevenness occurs in the coating. On the other hand, when the mass of the hydrophilic fine particles exceeds 20 g / m 2 , the mesh-like porous material is covered with the fine powder over the entire surface, and the mesh-like porous material is completely buried to reduce the surface area, resulting in poor hydrophilicity. Not only is it economical, but it can be easily peeled off by friction and vibration, causing a significant hindrance to mechanical strength.
　用いられる親水性の微粒子としては、コロイダルシリカ、コロイダルアルミナ、コロイド状のチタニア、ゼオライト、シリカゲル、シリカ、アルミナ、チタニア、炭酸カルシウム、酸化カルシウム、タルク、珪藻土、バーミキュライト、ヒル石、弁柄、貝殻焼成カルシウムおよびフィロケイ酸塩、金属微粒子等が上げられ、これらの群より選ばれる少なくとも一つが好適に用いられる。これら粒子の中で、珪藻土、ゼオライト、シリカゲル、貝殻焼成カルシウムおよびフィロケイ酸塩は、その多孔質性等のために吸水性、抗菌性等を発揮でき、本発明の物品の付加価値を高めることができ、好適であり、特には貝殻焼成カルシウムおよびフィロケイ酸塩の使用が好適である。これらの微粒子は組み合わせて使用することも可能で、たとえは、フィロケイ酸塩である雲母と金属微粒子の銀粒子を混合して懸濁液とすることもできる。 Examples of hydrophilic fine particles used include colloidal silica, colloidal alumina, colloidal titania, zeolite, silica gel, silica, alumina, titania, calcium carbonate, calcium oxide, talc, diatomaceous earth, vermiculite, leechite, petal, shell fired Calcium and phyllosilicates, metal fine particles, etc. are raised, and at least one selected from these groups is preferably used. Among these particles, diatomaceous earth, zeolite, silica gel, shell calcined calcium and phyllosilicate can exhibit water absorption, antibacterial properties and the like due to their porous properties, and increase the added value of the article of the present invention. Can be used, and the use of calcined shell calcium and phyllosilicates is particularly preferred. These fine particles can be used in combination. For example, mica, which is a phyllosilicate, and silver particles of metal fine particles can be mixed to form a suspension.
　貝殻焼成カルシウムは、比表面積が大きいので水の表面吸着性を増大させ親水性を長時間維持する効果を有する。さらには、それ自身カルシウム源として食品への添加の他、病原菌、細菌等の駆除剤用、野菜や果樹の残存農薬の洗浄用、医薬品用として利用されており、消毒効果、消臭効果、抗菌効果が期待できる。したがって、微粒子として貝殻焼成カルシウムを導入した場合、親水性の維持ばかりでなく抗菌作用という機能を付加することが可能となる。 Since the shell calcium calcined has a large specific surface area, it has the effect of increasing the water surface adsorption and maintaining the hydrophilicity for a long time. In addition to its own calcium source, it is also used as a source of calcium, as a pesticide for pathogens, bacteria, etc., for cleaning residual agricultural chemicals in vegetables and fruit trees, and as a pharmaceutical product. The effect can be expected. Accordingly, when shell calcined calcium is introduced as fine particles, it is possible to add not only the maintenance of hydrophilicity but also an antibacterial function.
　貝殻焼成カルシウムは、焼成前の主成分が炭酸カルシウムである貝殻を焼成することで、脱炭酸（二酸化炭素を取り除く）が徐々に進むことにより得られる、酸化カルシウム（ＣａＯ）又は、酸化カルシウムと炭酸カルシウムの混在したもののことである。焼成により、焼成前の主成分である炭酸カルシウム９９質量％が徐々に酸化カルシウムに変換されるが、併せて、焼成前の貝殻に含有している有機物１質量％の焼成も同時に進行する。焼成温度については、焼成温度を高くした場合には炭酸カルシウムが全て酸化カルシウムまで変換されるが、焼成温度が低い場合には、一部が酸化カルシウムに変わるが残りは炭酸カルシウムとして残る。 Calcium shell calcium is calcium oxide (CaO) or calcium oxide and carbonic acid obtained by gradually decarboxylation (removing carbon dioxide) by firing shells whose main component is calcium carbonate before firing. It is a mixture of calcium. By firing, 99% by mass of calcium carbonate, which is the main component before firing, is gradually converted into calcium oxide, and at the same time, firing of 1% by mass of organic matter contained in the shell before firing also proceeds simultaneously. Regarding the firing temperature, when the firing temperature is increased, all of the calcium carbonate is converted to calcium oxide, but when the firing temperature is low, part of the calcium carbonate is changed to calcium oxide, but the rest remains as calcium carbonate.
　用いる貝殻焼成カルシウムの成分については、特に限定されないが、炭酸カルシウムの一部が酸化カルシウムに変換できれば良く、本発明においては、具体的には、貝殻の主成分である炭酸カルシウムと、それを焼成することにより得られる酸化カルシウム、もしくは、酸化カルシウムと炭酸カルシウムの混在したもの又はそれぞれの混合状態（酸化カルシウムと炭酸カルシウムを混合）で用いることが好ましい。炭酸カルシウムと酸化カルシウム、各成分の割合は焼成温度および焼成時間により異なり、適宜、調整することができる。 The component of the calcined shell shell calcium to be used is not particularly limited as long as a part of the calcium carbonate can be converted to calcium oxide. In the present invention, specifically, calcium carbonate as the main component of the shell and the calcined product thereof. It is preferable to use calcium oxide obtained by doing this, a mixture of calcium oxide and calcium carbonate, or a mixed state thereof (mixed calcium oxide and calcium carbonate). The proportions of calcium carbonate and calcium oxide and each component differ depending on the firing temperature and firing time, and can be adjusted as appropriate.
　貝殻焼成カルシウムを製造する場合の焼成温度は、通常、５００℃～１２００℃である。好ましくは、６００℃～１１００℃の温度範囲内である。焼成時間については、焼成温度により異なるが、前述の貝殻焼成カルシウムを好ましい割合にするためには、適宜、調整することができる。 The calcination temperature when producing shell-calcined calcium is usually 500 ° C. to 1200 ° C. Preferably, it is in the temperature range of 600 ° C to 1100 ° C. The firing time varies depending on the firing temperature, but can be appropriately adjusted in order to obtain the above-mentioned shell-fired calcium in a preferred ratio.
　貝殻焼成カルシウムとして用いる貝殻はホタテ貝、アワビ、カキ、およびウバガイから少なくとも１種類以上が選択されている親水性被膜であることが好ましい。もちろん、本発明で用いられる貝殻としては、焼成前の成分が炭酸カルシウムを主成分として含有する貝殻であれば特に限定はなく、具体的には、赤貝、アサリ、ホタテ貝、アワビ、カキ、ウバガイ（ホッキ貝）、イモガイ、サクラガイ、サザエ、シジミ、タイラギ、タニシ、トリガイ、ハマグリ、バカガイ等が用いられる。しかし、特に好ましくは、ホタテ貝、アワビ、カキ、およびウバガイの貝殻である。 The shell used as the shell-calcined calcium is preferably a hydrophilic coating in which at least one kind is selected from scallops, abalone, oysters, and oysters. Of course, the shell used in the present invention is not particularly limited as long as the component before baking contains calcium carbonate as a main component, and specifically, red shellfish, clams, scallops, abalone, oysters, basilis. (Sea bream), mussels, cherry mussels, turban shells, rainbow trout, snails, snails, tiger oysters, clams, snails, etc. are used. However, particularly preferred are scallop, abalone, oyster, and crabs shells.
　フィロケイ酸塩は、アルミニウム、ナトリウム、カルシウム、マグネシウム等の金属イオンとケイ酸が連結して、四面体シート層状構造を形成することが特徴である。この四面体シート層状構造の隙間に金属イオン有機物等を交換する性質がありかつ、水を取り込む性質があるため、極めて良好な吸湿性を示すことが知られている。さらには、層状であることにより毛細管力、密着性、結束性の向上も期待できる。即ち、フィロケイ酸塩を微粒子として用いることにより、吸湿性の向上を含むこれらの新機能を付与できる。 The phyllosilicate is characterized in that metal ions such as aluminum, sodium, calcium, magnesium, etc. and silicic acid are linked to form a tetrahedral sheet layered structure. It is known that the interstices of the tetrahedral sheet layer structure have a property of exchanging metal ion organic substances and the like, and have a property of taking in water, and therefore exhibit extremely good hygroscopicity. Furthermore, improvement in capillary force, adhesion, and binding property can be expected due to the layered structure. That is, these new functions including improvement of hygroscopicity can be imparted by using phyllosilicate as fine particles.
　本発明に用いられるフィロケイ酸塩として雲母、セピオライトやモンモリロナイト、ハロサイト、カオリナイト、スメクタイト、タルク、バーミュキュライト、緑泥石、ガイロライト、ブレーナイト、珪孔雀、石ブドウ石、魚眼石、タルク、パイロフィライト、緑泥石、ディッカイト、蛇紋石、ゼオライト等があげられる。これらフィロケイ酸塩の中でも、粒子径、アスペクト比、入手のしやすさ、およびコストを勘案すれば、雲母（マイカ）、タルク、カオリナイトがより好ましい。 As phyllosilicate used in the present invention, mica, sepiolite, montmorillonite, halosite, kaolinite, smectite, talc, vermiculite, chlorite, gyrolite, branite, silicic peacock, stone pebbles, fisheye stone, talc Pyrophyllite, chlorite, dickite, serpentine, zeolite and the like. Among these phyllosilicates, mica, talc, and kaolinite are more preferable in consideration of the particle diameter, aspect ratio, availability, and cost.
　雲母としては、その形状や大きさによりさまざまな種類があり、例示するならば、白雲母、クロム白雲母、絹雲母、黒雲母、金雲母、フッ素金雲母、リチア雲母などが挙げられる。タルクは、滑石とも呼ばれ、ケイ酸マグネシウムの水和物（Ｍｇ3Ｓｉ4Ｏ10（ＯＨ）2）である。また、カオリナイト（Ａｌ2Ｓｉ2Ｏ5（ＯＨ）4、三斜晶系・単斜晶系　）はケイ酸アルミニウムの水和物であるが、類似のディク石（ｄｉｃｋｉｔｅ）、ナクル石もカオリンに含むものとする。 There are various types of mica depending on the shape and size, and examples include muscovite, chrome muscovite, sericite, biotite, phlogopite, fluorine phlogopite, and lithia mica. Talc is also called talc and is a hydrate of magnesium silicate (Mg 3 Si 4 O 10 (OH) 2 ). Kaolinite (Al 2 Si 2 O 5 (OH) 4 , triclinic / monoclinic) is a hydrate of aluminum silicate, but similar dictite and nakurite are also kaolin. To include.
　金属微粒子としては、金、銀、白金、パラジウム、ルテニウム、銅、ニッケル、バナジウム、チタン、インジウム、スズ、タングステン等のナノ金属粒子やナノ金属コロイド等が挙げられる。 Examples of the metal fine particles include nano metal particles such as gold, silver, platinum, palladium, ruthenium, copper, nickel, vanadium, titanium, indium, tin, and tungsten, and nano metal colloids.
　前記の微粒子を、水、メタノール、エタノール、ｉ－プロパノール、ｎ－プロパノール、ｎ－ブタノール、ｉ－ブタノール、ｔ－ブタノール、メトキシエタノール、エトキシエタノール等のアルコール類、エチレングリコール、酢酸エステル、カルボン酸、低級炭化水素、脂肪族、芳香族等の一般溶剤、又はこれらの混合物よりなる溶媒を用いて微粒子が懸濁化された懸濁液を調製する。また、分散性を改良するために分散剤等を添加してもよい。 The fine particles are mixed with water, methanol, ethanol, i-propanol, n-propanol, n-butanol, i-butanol, t-butanol, methoxyethanol, ethoxyethanol and other alcohols, ethylene glycol, acetate ester, carboxylic acid, A suspension in which the fine particles are suspended is prepared using a general solvent such as lower hydrocarbon, aliphatic, aromatic, or a mixture thereof. Moreover, you may add a dispersing agent etc. in order to improve a dispersibility.
　第一工程で得られた網目状多孔質構造体に当該微粒子を担持固定化する方法としては、微粒子を導入できるものであれば特に限定されず、上記懸濁液をコーティングする方法、または該懸濁液を含浸させる方法が挙げられる。 The method for supporting and immobilizing the fine particles on the network porous structure obtained in the first step is not particularly limited as long as the fine particles can be introduced. The method for coating the suspension or the suspension is not particularly limited. The method of impregnating a turbid liquid is mentioned.
　懸濁液をコーティングする方法としては、湿式ではディップコート、フローコート、スプレーコート、メッキ、無電界メッキ、スクリーン印刷、フレキソ印刷等の手段で行うことができ、ディップコート、スプレーコート、メッキ、無電界メッキが簡便な方法として好適に用いられる。 As a method of coating the suspension, wet coating can be performed by means of dip coating, flow coating, spray coating, plating, electroless plating, screen printing, flexographic printing, etc., and dip coating, spray coating, plating, no Electroplating is suitably used as a simple method.
　懸濁液のコーティングは乾式で行うこともでき、静電塗装法により帯電させた粉体を反対に帯電させた試料に衝突させて効率よく付着させる手法や、ブラスト法により親水性微粒子を高速で吹き付けて微細孔に緻密に塗布する手法が好的に用いられる。 Suspension coating can also be carried out dry, by applying a method in which the powder charged by the electrostatic coating method is made to collide with the oppositely charged sample for efficient adhesion, or the hydrophilic fine particles are applied at high speed by the blast method. A method of spraying and finely coating the fine holes is preferably used.
　懸濁液を含浸させる方法としては、常圧含浸法、減圧含浸法、加圧含浸法、ゾルゲル法、電気泳動法、浸漬超音波含浸法などがあり、常圧含浸法、減圧含浸法、加圧含浸法、浸漬超音波含親法が好適に用いられる。中でも、減圧加圧を併用する含浸法が好ましい。具体的な含浸法としては適当な真空容器中に網目状多孔質構造を形成したアルミニウム部材を置き、内部を減圧にしてから、当該微粒子の懸濁液を導入することによって表面細孔内に当該微粒子を密に充填することが出来る。また懸濁液を導入してから容器を加圧にしてより多くの微粒子を充填することもできる。また、浸漬超音波法も好適に用いられ、懸濁液に網目状多孔質構造を形成したアルミニウム部材を浸漬して、超音波をあてながら微粒子を導入するので、網目状多孔質構造の細部にまで微粒子が充填できる。 Methods for impregnating the suspension include atmospheric pressure impregnation method, reduced pressure impregnation method, pressure impregnation method, sol-gel method, electrophoresis method, immersion ultrasonic impregnation method, etc. A pressure impregnation method and an immersion ultrasonic parent method are preferably used. Among them, the impregnation method using pressure reduction and pressurization is preferable. As a specific impregnation method, an aluminum member having a network-like porous structure is placed in a suitable vacuum vessel, the pressure inside is reduced, and the suspension of the fine particles is introduced into the surface pores. The fine particles can be densely packed. It is also possible to fill the container with more fine particles by introducing the suspension and then pressurizing the container. In addition, the immersion ultrasonic method is also preferably used, and the fine particles are introduced while immersing the aluminum member in which the mesh-like porous structure is formed in the suspension and applying ultrasonic waves. Can be filled with fine particles.
　コーティングあるいは含浸により親水性微粒子を導入後、乾燥・加熱することにより、造膜することができ、親水性微粒子を担持固定することができる。乾燥・加熱処理方法は、特に限定されないが、常温で乾燥してもよいし、または熱風で加熱乾燥してもよい。また乾燥後にアルミニウムの基材を１００℃～５００℃まで加熱してさらに乾燥する手法も用いられ、例えば、室温で３０分乾燥後、１５０℃のオーブンで１時間程度加熱する方法が用いられる。このようにして、アルミニウム系複合親水性部材が製造できる。 After introducing the hydrophilic fine particles by coating or impregnation, the film can be formed by drying and heating, and the hydrophilic fine particles can be supported and fixed. The drying / heating treatment method is not particularly limited, and may be dried at room temperature or may be heated and dried with hot air. Further, a method of heating the aluminum base material to 100 ° C. to 500 ° C. after drying and further drying is also used. For example, a method of drying at room temperature for 30 minutes and then heating in an oven at 150 ° C. for about 1 hour is used. In this way, an aluminum based composite hydrophilic member can be produced.
　本発明の複合親水性部材においても親水性部材の場合と同様、その純水接触角は３０度以下であることが望ましい。その純水接触角が３０度を超えると、所定の親水性が得られないからである。より好ましくは２０度以下、さらに好ましくは１０度以下である。得られた複合親水性部材の純水接触角を測定すると、水滴は被膜表面を広がり、便宜上接触角が０°として測定され、被膜が超親水性であることが観察できる。 In the composite hydrophilic member of the present invention, the pure water contact angle is desirably 30 degrees or less, as in the case of the hydrophilic member. This is because if the pure water contact angle exceeds 30 degrees, the predetermined hydrophilicity cannot be obtained. More preferably, it is 20 degrees or less, and more preferably 10 degrees or less. When the contact angle of pure water of the obtained composite hydrophilic member is measured, water droplets spread on the surface of the coating, and the contact angle is measured as 0 ° for convenience, and it can be observed that the coating is superhydrophilic.
　また、本発明者らは「水酸化リチウムを含む塩基性混合溶液」に「親水性微粒子」を混合してなる溶液または懸濁液を用いてアルミニウム系材料を処理することにより、網目状多孔質構造体が形成される側から親水性微粒子が速やかに担持され、簡単なプロセスにより親水性微粒子がより強固に担持された密着性に優れる親水性部材が得られることを見出した。 Further, the present inventors treated the aluminum-based material with a solution or suspension obtained by mixing “hydrophilic fine particles” with “basic mixed solution containing lithium hydroxide”, thereby forming a mesh-like porous material. It has been found that a hydrophilic member excellent in adhesion can be obtained in which hydrophilic fine particles are rapidly supported from the side on which the structure is formed, and the hydrophilic fine particles are more firmly supported by a simple process.
　なお、コロイダル金属酸化物やフィロ珪酸塩等の親水性微粒子は、アルカリ金属の水酸化物と反応することは当業者にも知られており、反応により形態の違う塩を形成する可能性もあり、親水性微粒子を水酸化リチウムを含む塩基性混合溶液に混合懸濁させることは通常は行われないプロセスである。 In addition, it is known to those skilled in the art that hydrophilic fine particles such as colloidal metal oxides and phyllosilicates react with alkali metal hydroxides, and there is a possibility of forming different forms of salts depending on the reaction. Mixing and suspending hydrophilic fine particles in a basic mixed solution containing lithium hydroxide is a process that is not normally performed.
　次いで、本発明のアルミニウムもしくはその合金を、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液に親水性微粒子を混合してなる溶液または懸濁液で処理することにより、アルミニウムもしくはその合金の表層部の少なくとも一部に網目状多孔質構造体を担体として形成するとともに、当該担体に前記親水性微粒子を担持固定させることを特徴とするアルミニウム系親水性部材について説明する。 Next, by treating the aluminum of the present invention or an alloy thereof with a solution or suspension obtained by mixing hydrophilic fine particles in a basic mixed solution obtained by mixing a base containing lithium hydroxide, water and an organic solvent, A description will be given of an aluminum-based hydrophilic member characterized in that a network-like porous structure is formed as a carrier on at least a part of the surface layer of aluminum or an alloy thereof, and the hydrophilic fine particles are supported and fixed on the carrier.
　本発明においては、網目状多孔質構造体が形成しながら同時に親水性微粒子が多孔質体の凹凸表面や、多孔質空隙内部に速やかに親水性微粒子が担持されるため、より簡単な１回の工程で製造できるばかりでなく、親水性微粒子がより強固に担持された密着性に優れる親水性部材が得られるという効果を奏する。 In the present invention, the hydrophilic fine particles are rapidly carried on the uneven surface of the porous body or inside the porous voids while the network-like porous structure is formed. In addition to being manufactured in the process, there is an effect that a hydrophilic member excellent in adhesiveness in which hydrophilic fine particles are more firmly supported is obtained.
アルミニウム系材料は、前述のものが好適に使用される。 As the aluminum material, those described above are preferably used.
尚、混合溶媒には前述の溶媒を混合したものを用いて、同じように調整した、同様の性質を持つ物を使用し、それに親水性微粒子を添加する。 In addition, the mixed solvent is a mixture of the above-mentioned solvents, and the same adjusted material having the same properties is used, and hydrophilic fine particles are added thereto.
　微粒子の粒子径は、特に限定はされないが、５ｎｍ～５０μｍの範囲内にあることが好ましい。平均粒径が５ｎｍ未満であると、微粒子の粒径が小さ過ぎて長期の塗布時間が必要で効率が悪くまた、微粒子の有する表面エネルギーが非常に大きくなり、単分散が困難で凝集しやすく取り扱いが非常に困難である。一方、微粒子の平均粒径が５０μｍを越えると、被膜上の網目状多孔質構造体の孔径よりも遥かに大きくなるために重力の影響が大きくなり孔径中に取り込まれた微粒子が保持しきれなくなり、摩擦により容易に剥がれてしまう等の問題が発生する。より好ましくは０．５μｍ～４０μｍ、さらに好ましくは０．０５μｍ～２０μｍである。 The particle diameter of the fine particles is not particularly limited, but is preferably in the range of 5 nm to 50 μm. If the average particle size is less than 5 nm, the particle size of the fine particles is too small, requiring a long coating time, resulting in poor efficiency. Also, the surface energy of the fine particles becomes very large, making monodispersion difficult and easy to aggregate. Is very difficult. On the other hand, if the average particle size of the fine particles exceeds 50 μm, the influence of gravity increases because the particle size is much larger than the pore size of the mesh-like porous structure on the coating, and the fine particles incorporated in the pore size cannot be retained. The problem of peeling off easily due to friction occurs. More preferably, it is 0.5 μm to 40 μm, and still more preferably 0.05 μm to 20 μm.
　なお、ここでいう粒子の粒径は所謂１次粒子の大きさを示し、微粒子同士が凝集した２次粒子の大きさを示しているのではない。親水膜においては、２次粒子の大きさは成膜に困難がなければ、特に限定されるものではない。 Note that the particle size of the particles referred to here indicates the size of so-called primary particles, and does not indicate the size of secondary particles in which fine particles are aggregated. In the hydrophilic film, the size of the secondary particles is not particularly limited as long as there is no difficulty in film formation.
　本発明でアルミニウム材料を処理する薬液は、上記塩基性混合溶液と上記親水性微粒子を混合してなる溶液または懸濁液（以下、「微粒子混合液」という）である。親水性微粒子は、親水性ゾルとして混合することもできる。親水性微粒子の混合量は当該微粒子が形成される多孔質体に良好に担持可能であれば特に限定されないが、塩基性混合用液に対して０．０１質量％～２０質量％が適当である。０．０１質量％よりも少なければ希薄すぎて充分な担持ができなくなり、２０質量％よりも多い場合は粘度が高くなりすぎて操作性が悪くなるばかりでなく、担持されない微粒子が多くなり無駄である。 The chemical solution for treating an aluminum material according to the present invention is a solution or suspension (hereinafter referred to as “fine particle mixed solution”) obtained by mixing the basic mixed solution and the hydrophilic fine particles. The hydrophilic fine particles can be mixed as a hydrophilic sol. The mixing amount of the hydrophilic fine particles is not particularly limited as long as it can be favorably supported on the porous body on which the fine particles are formed, but 0.01% by mass to 20% by mass with respect to the basic mixing liquid is appropriate. . If it is less than 0.01% by mass, it is too dilute and cannot be fully supported. If it is more than 20% by mass, the viscosity becomes too high and the operability is deteriorated. is there.
　調製した微粒子混合液は、含有する親水性微粒子が塩基性混合溶液に均一に分散していることが望ましく、攪拌や超音波を照射する等の処理を行うのがよい。　 The prepared fine particle mixed solution desirably contains the hydrophilic fine particles contained therein uniformly in the basic mixed solution, and is preferably subjected to a treatment such as stirring or irradiation with ultrasonic waves. *
　本発明においてアルミニウム系材料を上記微粒子混合液で処理するにあたり、アルミニウム系材料を微粒子混合液と接触させる必要がある。 In the present invention, when the aluminum-based material is treated with the fine particle mixed solution, the aluminum-based material needs to be brought into contact with the fine particle mixed solution.
　前述のように、アルミニウム系材料の表面は酸化アルミニウムの被膜により撥水性を有するので、薬液との濡れ性が悪い場合は、被膜除去の処理を行うことがある。一般には脱脂洗浄や、サンドペーパー掛け、サンドブラスト掛け、アーク照射、プラズマ処理等の表面活性処理を行うが、表面活性処理時のムラにより均一に処理されない場合がある。本発明の親水性部材にかかる製造においては、有機溶媒を用いて微粒子混合液の表面張力を低くすることにより、アルミニウム表面との濡れ性が改善されるため、表面処理時のムラに関係なく均一に反応させることが可能である。また、水酸化リチウムを含む塩基性混合溶液がある程度の脱脂力を有しているため、微粒子混合液を用いることにより、脱脂洗浄や表面活性処理を省略することができる。 As described above, since the surface of the aluminum-based material has water repellency due to the aluminum oxide film, the film removal treatment may be performed when the wettability with the chemical solution is poor. In general, surface activation treatment such as degreasing cleaning, sandpaper application, sandblasting, arc irradiation, plasma treatment, etc. is performed, but there are cases where uniform treatment is not possible due to unevenness during the surface activation treatment. In the production of the hydrophilic member of the present invention, the wettability with the aluminum surface is improved by lowering the surface tension of the fine particle mixture using an organic solvent, so that it is uniform regardless of unevenness during the surface treatment. It is possible to react. Moreover, since the basic mixed solution containing lithium hydroxide has a certain degree of degreasing power, degreasing and surface activation treatment can be omitted by using the fine particle mixed solution.
　アルミニウム系材料を微粒子混合液と接触させる方法は、特に限定されないが、当該微粒子混合液をスプレー等で吹き付ける方法、シリンジ等で滴下する方法、微粒子混合液の処理浴の中に浸漬（含浸も含む）する方法が挙げられるが、処理浴に浸漬する方法が好適に用いられる。 The method of bringing the aluminum-based material into contact with the fine particle mixed solution is not particularly limited, but the method of spraying the fine particle mixed solution with a spray or the like, the method of dropping with a syringe, or the like (including impregnation) ), But a method of immersing in a treatment bath is preferably used.
　浸漬（含浸も含む）においては、常圧、減圧または加圧下で行うことができる。また、浸漬超音波法も好適に用いられ、微粒子混合液にアルミニウム材料を浸漬して、超音波をあてながら処理することも可能である。 Immersion (including impregnation) can be performed under normal pressure, reduced pressure, or increased pressure. In addition, an immersion ultrasonic method is also preferably used, and it is possible to immerse an aluminum material in a fine particle mixture and perform the treatment while applying ultrasonic waves.
　処理浴への浸漬時間は、アルミニウム系材料の種類、形状、寸法、および微粒子混合液の濃度、組成、浴温等に応じて適当な時間を選べばよく、通常は３０秒～１５分に設定される。また、浴温についても、浸漬時間との兼ね合いにより、適当な温度に設定すればよいが、通常は、微粒子混合液は、常温～５０℃程度に設定され、より好適には、２０℃～４０℃に設定される。上記温度範囲よりも低いと、反応の進行に要する時間が非常に長くなり、反対に高いと、反応が速くなりすぎて、被膜が激しく侵食されたり、網目状多孔質構造が破壊されたり、表面が不均一になりやすく好ましくない。 The immersion time in the treatment bath may be selected appropriately depending on the type, shape and dimensions of the aluminum-based material and the concentration, composition, bath temperature, etc. of the fine particle mixture, and is usually set to 30 seconds to 15 minutes. Is done. Also, the bath temperature may be set to an appropriate temperature in consideration of the immersion time. Usually, the fine particle mixed solution is set to room temperature to about 50 ° C., and more preferably 20 ° C. to 40 ° C. Set to ° C. When the temperature is lower than the above temperature range, the time required for the reaction to proceed is very long. On the other hand, when the temperature is high, the reaction becomes too fast, the coating is eroded violently, the mesh porous structure is destroyed, the surface Tends to be non-uniform.
　アルミニウム材料を浸漬させると、アルミニウムと水酸化リチウムの反応が進行し、浸漬後３０秒～５分でアルミニウム材料表面から微細な水素発泡が観察される。目安として発泡してから３０秒～５分の時間浸漬させることにより適度な反応を行わせることができる。 When the aluminum material is immersed, the reaction between aluminum and lithium hydroxide proceeds, and fine hydrogen foaming is observed from the surface of the aluminum material 30 seconds to 5 minutes after immersion. As a guide, moderate reaction can be performed by dipping for 30 seconds to 5 minutes after foaming.
　微粒子混合液でアルミニウム材料を処理することにより、アルミニウム材料と塩基性混合用液とが反応し、アルミニウム材料の表面に孔径５～５００ｎｍの網目状多孔質構造体が形成される。親水性微粒子は、当該多孔質構造体の孔径にフィットするようにアンカーとして担持され、共に親水性である微粒子と多孔質構造体が付着するため強固な密着性を有する。本発明では、当該多孔質体が形成される側から上記親水性微粒が担持されるため、２工程にわたる担持固定と比較してより密着性に優れる効果を奏する。 By treating the aluminum material with the fine particle mixed solution, the aluminum material and the basic mixing solution react to form a network-like porous structure having a pore diameter of 5 to 500 nm on the surface of the aluminum material. The hydrophilic fine particles are supported as anchors so as to fit the pore size of the porous structure, and have both strong adhesion because the hydrophilic fine particles and the porous structure adhere to each other. In this invention, since the said hydrophilic fine particle is carry | supported from the side in which the said porous body is formed, there exists an effect which is excellent in adhesiveness compared with the carrying | fixing fixation over 2 processes.
　用いる無機微粒子の中には、５００ｎｍより大きい粒子径を有するものがあるが、アンカーとして孔内に入った無機微粒子の最表面の部分とそれよりも大きい無機微粒子間での強固な結合が形成されるため、孔内の微粒子が膜の外側の粒子を保持する形で、複雑な表面を形成し比表面積の大きい被膜で覆われるものと思われる。当該被膜は親水性微粒子で構成されるため、優れた親水性が発現し、アルミニウム系親水性複合部材として有用である。 Some of the inorganic fine particles used have a particle diameter larger than 500 nm, but a strong bond is formed between the outermost surface portion of the inorganic fine particles that have entered the hole as an anchor and the larger inorganic fine particles. Therefore, it is considered that the fine particles in the pores hold the particles outside the membrane, form a complex surface, and are covered with a coating having a large specific surface area. Since the coating is composed of hydrophilic fine particles, it exhibits excellent hydrophilicity and is useful as an aluminum-based hydrophilic composite member.
　本発明において、担持される親水性微粒子の単位面積当たりの質量は０．１ｇ／ｍ2～２０ｇ／ｍ2の範囲内にあることが必要である。この親水性微粒子の単位面積当たりの質量が０．１ｇ／ｍ2未満の場合には充分な被覆がなされず、被覆にムラが生じるため好ましくない。一方、親水性微粒子の質量が２０ｇ／ｍ2を超える場合には、網目状多孔質が微粉末で全面にわたって被覆され、完全に網目状多孔質が埋没して表面積が低下するため親水性が劣るばかりか経済的ではなく、摩擦や振動で容易に剥離脱落して機械的強度に著しく支障をきたす In the present invention, the mass per unit area of the hydrophilic fine particles to be supported needs to be within the range of 0.1 g / m 2 to 20 g / m 2 . If the mass per unit area of the hydrophilic fine particles is less than 0.1 g / m 2 , it is not preferable because sufficient coating is not performed and unevenness occurs in the coating. On the other hand, when the mass of the hydrophilic fine particles exceeds 20 g / m 2 , the mesh-like porous material is covered with the fine powder over the entire surface, and the mesh-like porous material is completely buried to reduce the surface area, resulting in poor hydrophilicity. Not only economical, but it can be easily peeled off due to friction and vibration, causing a significant hindrance to mechanical strength.
　上記の処理の後に、乾燥・加熱することにより、造膜することができ、親水性微粒子を担持固定することができる。乾燥・加熱処理方法は、特に限定されないが、常温で乾燥してもよいし、または熱風で加熱乾燥してもよい。また乾燥後にアルミニウムの基材を１００℃～５００℃まで加熱してさらに乾燥する手法も用いられ、例えば、室温で３０分乾燥後、１５０℃のオーブンで１時間程度加熱する方法が用いられる。このようにして、アルミニウム系複合親水性部材が製造できる。 After the above treatment, the film can be formed by drying and heating, and hydrophilic fine particles can be supported and fixed. The drying / heating treatment method is not particularly limited, and may be dried at room temperature or may be heated and dried with hot air. Further, a method of heating the aluminum base material to 100 ° C. to 500 ° C. after drying and further drying is also used. For example, a method of drying at room temperature for 30 minutes and then heating in an oven at 150 ° C. for about 1 hour is used. In this way, an aluminum based composite hydrophilic member can be produced.
　本発明の処理により得られるアルミニウム系親水性部材の表面を走査型電子顕微鏡で観察したところ、孔径５ｎｍ～５００ｎｍ、深さ０．０５μｍ～１０μｍの規則正しく並んだ網目状多孔質体の細孔に親水性微粒子が担持されていることが判った。 The surface of the aluminum-based hydrophilic member obtained by the treatment of the present invention was observed with a scanning electron microscope. It was found that the fine particles were supported.
　本発明の親水性部材において、その純水接触角は３０度以下であることが望ましい。その純水接触角が３０度を超えると、所定の親水性が得られないからである。より好ましくは２０度以下、さらに好ましくは１０度以下である。ここで、純水接触角が３０度以下としたのは、例えば純水接触角が５度よりも小さくなると、高精度の測定は難しくなるが、極めて０°に近い純水接触角の親水性示す場合も含むからである。本明細書では、１０°以下の純粋接触角を示す場合、「超親水性」と評価する。なお、純水接触角の測定は、ＪＩＳＲ３２５７「基板ガラス表面の濡れ性試験方法」に準じて行われる。 In the hydrophilic member of the present invention, the pure water contact angle is desirably 30 degrees or less. This is because if the pure water contact angle exceeds 30 degrees, the predetermined hydrophilicity cannot be obtained. More preferably, it is 20 degrees or less, and more preferably 10 degrees or less. Here, the pure water contact angle is set to 30 degrees or less. For example, when the pure water contact angle is less than 5 degrees, high-precision measurement becomes difficult, but the hydrophilicity of the pure water contact angle is extremely close to 0 °. It is because the case where it shows is also included. In this specification, when a pure contact angle of 10 ° or less is exhibited, it is evaluated as “superhydrophilic”. The pure water contact angle is measured according to JIS R3257 “Testing method for wettability of substrate glass surface”.
　本発明の網目状多孔質構造に親水性微粒子を担持させたアルミニウム系部材の純水接触角を測定すると、水滴は被膜表面を広がり、接触角が測定できない程度に小さくなり、被膜が超親水性であることが観察できる。 When the pure water contact angle of the aluminum-based member having hydrophilic fine particles supported on the network porous structure of the present invention is measured, the water droplet spreads on the surface of the film, the contact angle cannot be measured, and the film is superhydrophilic. Can be observed.
　次に、実施例について比較例と併せて説明するが、これらに限定されるものではない。なお、測定においては、以下の測定器を使用した。 Next, examples will be described together with comparative examples, but are not limited thereto. In the measurement, the following measuring devices were used.
「走査型電子顕微鏡」
　ＦＥ－ＳＥＭ　日立製　Ｓ－４５００型　　加速電圧　１０ｋｖ　
「純水接触角測定」
　協和界面科学製　接触角計（型式ＣＡ－Ｘ型）
　（純水１０μｌを表面に滴下して接触角を測定）
「走査型電子顕微鏡」　(ＳＥＭ)
　ＦＥ－ＳＥＭ　日立製　Ｓ－４５００型　　加速電圧　１０ｋｖ "Scanning electron microscope"
FE-SEM Hitachi S-4500 acceleration voltage 10kv
"Pure water contact angle measurement"
Kyowa Interface Science contact angle meter (model CA-X)
(Measure the contact angle by dropping 10 μl of pure water on the surface)
"Scanning electron microscope" (SEM)
FE-SEM Hitachi S-4500 acceleration voltage 10kv
最初に、アルミニウム系材料に化学的な処理を施し、細孔を形成させることを目的として一連の研究を重ねる過程で、アルミニウム系材料を、水酸化リチウムを含む塩基と水と有機溶媒を混合した塩基性混合溶液（特に特定の表面張力を有する塩基性混合溶液）で処理することにより、アルミニウム系材料の表面との濡れ性が改善され、アルミニウム表面と水酸化リチウムの速やかな反応が進行して、表層部の少なくとも一部に酸化被膜とは異なる網目状多孔質構造体が形成されることを確かめた。以下、実施例１～６に示す。 First, in the process of carrying out a series of studies for the purpose of chemically treating the aluminum-based material and forming pores, the aluminum-based material was mixed with a base containing lithium hydroxide, water, and an organic solvent. By treating with a basic mixed solution (especially a basic mixed solution having a specific surface tension), the wettability with the surface of the aluminum-based material is improved, and a rapid reaction between the aluminum surface and lithium hydroxide proceeds. It was confirmed that a network-like porous structure different from the oxide film was formed on at least a part of the surface layer portion. Examples 1 to 6 are shown below.
「実施例１」　アルミニウム板　（水酸化リチウム／水／ＥｔＯＨ系）
　水酸化リチウム一水和物（ＬｉＯＨ・Ｈ2Ｏ：和光特級試薬）を３００ｍｌビーカーに６．０ｇ（０．１４ｍｏｌ）秤り取り、次いでイオン交換水１００ｍｌを加えて常温で攪拌し溶解させた。さらに特級エタノール１００ｍｌを攪拌しながら徐々に添加して、１．９質量％の濃度の水酸化リチウム処理溶液を調製した。当該処理溶液のｐＨは、１１．１であった。 "Example 1" Aluminum plate (lithium hydroxide / water / EtOH system)
Lithium hydroxide monohydrate (LiOH.H 2 O: Wako Special Grade Reagent) was weighed out in a 300 ml beaker, 6.0 g (0.14 mol) was added, and then 100 ml of ion-exchanged water was added and stirred at room temperature for dissolution. Further, 100 ml of special grade ethanol was gradually added with stirring to prepare a lithium hydroxide treatment solution having a concentration of 1.9% by mass. The pH of the treatment solution was 11.1.
アルミニウム系材料として、純度９９．５質量％のアルミニウム基材Ａ１０５０の平板（厚さ０．１ｍｍ、サイズ１００ｍｍ×１００ｍｍ）を、上記のとおりに調製した水酸化リチウム混合溶液に２５℃で浸漬させた。浸漬後３０秒でアルミニウム基材表面から微細な水素の発泡が観察された。約１分間浸漬した後、４ｍｍ／ｓｅｃで引き上げて、次いで室温で３０分間乾燥させた。乾燥後、蒸留水で充分にすすぎ、室温にて再度乾燥させた。表面の微細構造を走査型電子顕微鏡で観察したところ、図１に示すように表面に均一の網目微細構造体が形成していた。 As an aluminum-based material, a flat plate (thickness 0.1 mm, size 100 mm × 100 mm) of an aluminum base material A1050 having a purity of 99.5% by mass was immersed in a lithium hydroxide mixed solution prepared as described above at 25 ° C. . Fine hydrogen foaming was observed from the surface of the aluminum substrate 30 seconds after the immersion. After being immersed for about 1 minute, it was pulled up at 4 mm / sec and then dried at room temperature for 30 minutes. After drying, it was rinsed thoroughly with distilled water and dried again at room temperature. When the fine structure of the surface was observed with a scanning electron microscope, a uniform network fine structure was formed on the surface as shown in FIG.
「実施例２」　アルミニウム板　（水酸化リチウム／水／ＭｅＯＨ系）
　水酸化リチウム一水和物（ＬｉＯＨ・Ｈ2Ｏ：和光特級試薬）を３００ｍｌビーカーに８．０ｇ（０．１９ｍｏｌ）秤り取り、次いでイオン交換水１００ｍｌを加えて常温で攪拌し溶解させた。さらに特級メタノール１００ｍｌを攪拌しながら徐々に添加して、２．５質量％の濃度の水酸化リチウム処理溶液を調製した。当該処理溶液のｐＨは、１１．３であった。 "Example 2" Aluminum plate (lithium hydroxide / water / MeOH system)
8.0 g (0.19 mol) of lithium hydroxide monohydrate (LiOH.H 2 O: Wako Special Grade Reagent) was weighed into a 300 ml beaker, and then 100 ml of ion exchange water was added and stirred at room temperature to dissolve. Further, 100 ml of special grade methanol was gradually added while stirring to prepare a lithium hydroxide treatment solution having a concentration of 2.5% by mass. The pH of the treatment solution was 11.3.
　アルミニウム系材料として、純度９９．５質量％のアルミニウム基材Ａ１０５０の平板（厚さ０．１ｍｍ、サイズ１００ｍｍ×１００ｍｍ）を、上記のとおりに調製した水酸化リチウム混合溶液に２５℃で浸漬させた。浸漬後３０秒でアルミニウム基材表面から微細な水素の発泡が観察された。約１分間浸漬した後、２ｍｍ／ｓｅｃで引き上げて、次いで室温で３０分間乾燥させた。乾燥後、蒸留水で充分にすすぎ、室温にて再度乾燥させた。表面の微細構造を走査型電子顕微鏡で観察したところ、表面に均一の網目微細構造体が形成していた。 As an aluminum-based material, a flat plate (thickness 0.1 mm, size 100 mm × 100 mm) of an aluminum base material A1050 having a purity of 99.5% by mass was immersed in a lithium hydroxide mixed solution prepared as described above at 25 ° C. . Fine hydrogen foaming was observed from the surface of the aluminum substrate 30 seconds after the immersion. After being immersed for about 1 minute, it was pulled up at 2 mm / sec and then dried at room temperature for 30 minutes. After drying, it was rinsed thoroughly with distilled water and dried again at room temperature. When the fine structure of the surface was observed with a scanning electron microscope, a uniform network fine structure was formed on the surface.
「実施例３」　アルミニウム板　（水酸化リチウム／水／イソプロパノール系）
　水酸化リチウム一水和物（ＬｉＯＨ・Ｈ2Ｏ：和光特級試薬）を３００ｍｌビーカーに５．０ｇ（０．１２ｍｏｌ）秤り取り、次いでイオン交換水１４０ｍｌを加えて常温で攪拌し溶解させた。さらに特級イソプロパノール６０ｍｌを攪拌しながら徐々に添加して、１．５質量％の濃度の水酸化リチウム処理溶液を調製した。この溶液を５０℃に加温して処理液とした。処理液のｐＨは１１．０であった。 "Example 3" Aluminum plate (lithium hydroxide / water / isopropanol system)
Lithium hydroxide monohydrate (LiOH.H 2 O: Wako Special Grade Reagent) was weighed out in a 300 ml beaker by 5.0 g (0.12 mol), and then 140 ml of ion-exchanged water was added and stirred at room temperature for dissolution. Further, 60 ml of special grade isopropanol was gradually added with stirring to prepare a lithium hydroxide treatment solution having a concentration of 1.5% by mass. This solution was heated to 50 ° C. to prepare a treatment solution. The pH of the treatment liquid was 11.0.
　アルミニウム系材料として、純度９９．５質量％のアルミニウム基材：Ａ１０５０の平板（厚さ０．１ｍｍ、サイズ１００ｍｍ×１００ｍｍ）を、上記調製した５０℃の水酸化リチウム混合溶液に浸漬させた。浸漬後２０秒でアルミニウム基材表面から微細な水素の発泡が観察された。約１分間浸漬した後、５ｍｍ／ｓｅｃで引き上げて、次いで室温で２０分間乾燥させた。乾燥後、蒸留水で充分にすすぎ、室温にて再度乾燥させた。表面の微細構造をＳＥＭで観察したところ、表面に均一の網目微細構造体が形成していた。 As an aluminum-based material, an aluminum substrate having a purity of 99.5% by mass: A 1050 flat plate (thickness 0.1 mm, size 100 mm × 100 mm) was immersed in the lithium hydroxide mixed solution prepared above at 50 ° C. Fine hydrogen foaming was observed from the surface of the aluminum substrate 20 seconds after the immersion. After being immersed for about 1 minute, it was pulled up at 5 mm / sec and then dried at room temperature for 20 minutes. After drying, it was rinsed thoroughly with distilled water and dried again at room temperature. When the surface microstructure was observed with an SEM, a uniform network microstructure was formed on the surface.
「実施例４」　アルミニウム金属不織布　（水酸化リチウム／水／ＥｔＯＨ系）
　アルミニウム系材料として、繊維の平均径が１５０μｍ、目付け量１．５ｋｇ／ｍ2、厚みが１ｍｍのアルミニウム金属不織布（商品名「メタシリー」、株式会社サーマル製）を用いて、実施例１で調製した水酸化リチウム処理溶液に上記アルミニウム金属不織布を２５℃で浸漬させた。浸漬後３０秒でアルミニウム基材表面から微細な水素発泡が見られ、約1分間保持した後、４ｍｍ／ｓｅｃで引き上げて、室温で３０分間乾燥させた。乾燥後充分に蒸留水ですすぎ表面の微細構造を走査型電子顕微鏡で観察したところ、表面が均一の網目微細構造が形成されていた（図２）。 "Example 4" Aluminum metal nonwoven fabric (lithium hydroxide / water / EtOH system)
Prepared in Example 1 using an aluminum metal nonwoven fabric (trade name “METACILY”, manufactured by Thermal Corporation) having an average fiber diameter of 150 μm, a basis weight of 1.5 kg / m 2 , and a thickness of 1 mm as an aluminum-based material. The said aluminum metal nonwoven fabric was immersed in the lithium hydroxide processing solution at 25 degreeC. Fine hydrogen foaming was observed from the surface of the aluminum substrate 30 seconds after the immersion, and after holding for about 1 minute, it was pulled up at 4 mm / sec and dried at room temperature for 30 minutes. When the fine structure of the surface was observed with a scanning electron microscope after thoroughly rinsing with distilled water after drying, a network fine structure with a uniform surface was formed (FIG. 2).
「実施例５」　機能性アルミニウム部材の製造（ゼオライトの担持）
　実施例４で得られた、表面に網目状多孔質構造を有するアルミニウム金属不織布に浸漬超音波含浸法にてゼオライト粒子の担持を行った。 "Example 5" Production of functional aluminum member (support of zeolite)
Zeolite particles were supported by the immersion ultrasonic impregnation method on the aluminum metal nonwoven fabric having a mesh-like porous structure on the surface obtained in Example 4.
　２００ｍｌのビーカーにゼオラム（東ソー・ゼオラム株式会社製）を５ｇとり、純水１００ｍｌを加え、株式会社サンテック製ＵＸ－３００型超音波分散機にて６０分間分散させ、懸濁液を調製した。実施例４で得られた表面に網目状多孔質構造を有するアルミニウム金属不織布を上記懸濁液に１分浸漬させた後、３ｍｍ／ｓｅｃで引き上げて、１２０℃で１時間乾燥させた。乾燥後、表面の微細構造をＳＥＭで観察したところ、図３に示すように、網目状多孔質構造中にゼオライト微粒子が９．０ｇ／ｍ2で均一に埋め込まれていた。 In a 200 ml beaker, 5 g of Zeolum (manufactured by Tosoh Zeolum Co., Ltd.) was added, 100 ml of pure water was added, and the mixture was dispersed for 60 minutes with a UX-300 type ultrasonic disperser manufactured by Suntech Co., Ltd. The aluminum metal nonwoven fabric having a network porous structure on the surface obtained in Example 4 was immersed in the suspension for 1 minute, then pulled up at 3 mm / sec and dried at 120 ° C. for 1 hour. When the surface microstructure was observed by SEM after drying, zeolite fine particles were uniformly embedded at 9.0 g / m 2 in the network porous structure as shown in FIG.
「実施例６」　　
　上記実施例５で得られた、表面に形成した網目状多孔質構造にゼオライトを埋め込み吸着性を付与したアルミニウム不織布部材を用いて、アルデヒドの吸着性試験を行った。
ａ．試験方法　　
　コック付きの１０Ｌデシケータに、実施例５で得られたゼオライトを担持したアルミニウム不織布を入れた。デシケータのコックを開き、シリンジにてアセトアルデヒドを注入し、初期濃度１５０ｐｐｍになるように調節した。初期値としてアセトアルデヒドの濃度を測定したところ１４３ｐｐｍであった。１時間経過後に、コックより気体を採取してアセトアルデヒドの濃度を測定したところ、８２ｐｐｍに減少していた。さらに３時間後に同様に測定したところ２１ｐｐｍ、２４時間経過後では２ｐｐｍに低減しており、アセトアルデヒドがアルミニウム不織布網目状多孔質構造のゼオライトに吸着されたことが認められた。 "Example 6"
The aldehyde adsorptivity test was conducted using the aluminum nonwoven fabric member obtained by embedding zeolite in the mesh porous structure formed on the surface and imparting the adsorptivity.
a. Test method
The aluminum nonwoven fabric carrying the zeolite obtained in Example 5 was placed in a 10 L desiccator with a cock. The cock of the desiccator was opened and acetaldehyde was injected with a syringe to adjust the initial concentration to 150 ppm. When the concentration of acetaldehyde was measured as an initial value, it was 143 ppm. After 1 hour, gas was sampled from the cock and the concentration of acetaldehyde was measured. As a result, it was reduced to 82 ppm. Further, when the same measurement was made after 3 hours, it was reduced to 21 ppm and after 24 hours, it was reduced to 2 ppm, and it was confirmed that acetaldehyde was adsorbed on the zeolite of the aluminum nonwoven fabric network porous structure.
「比較例１」　アルミニウム板（ＬｉＯＨ／水／水系）の場合
　特級エタノールの代わりに水を用いた以外は実施例１と同様な方法で、１．９質量％の濃度の水酸化リチウム水溶液を調製した。実施例１と同様に純度９９．５質量％のアルミニウム基材Ａ１０５０の平板（厚さ０．１ｍｍ、サイズ１００ｍｍ×１００ｍｍ）を、上記１．９質量％の濃度の水酸化リチウム水溶液に２５℃で１分間浸漬し、次いで室温で３０分乾燥、水洗浄、室温にて再乾燥処理を行った。得たれたアルミニウム板の表面を目視により観察したところ、反応により白くなった部分と未反応と思われる光沢の部分がまだら状に存在していた。アルミニウム表面との均一な反応は進行せず、部分的に未反応な部分が残ったものと思われる。 "Comparative example 1" In the case of an aluminum plate (LiOH / water / water system) A lithium hydroxide aqueous solution having a concentration of 1.9% by mass was prepared in the same manner as in Example 1 except that water was used instead of special grade ethanol. did. As in Example 1, a flat plate (thickness 0.1 mm, size 100 mm × 100 mm) of an aluminum substrate A1050 having a purity of 99.5% by mass was placed in an aqueous lithium hydroxide solution having a concentration of 1.9% by mass at 25 ° C. It was immersed for 1 minute, then dried at room temperature for 30 minutes, washed with water, and re-dried at room temperature. When the surface of the obtained aluminum plate was observed with the naked eye, a whitened portion due to the reaction and a glossy portion that seemed to be unreacted were present in a mottled manner. It seems that the uniform reaction with the aluminum surface does not proceed and a partially unreacted portion remains.
「比較例２」　アルミニウム板（ＮａＯＨ／ＥｔＯＨ／水系）の場合
水酸化リチウムの代替に水酸化ナトリウムを用いた以外は実施例１と同様な方法で、１．９質量％の濃度の水酸化ナトリウム／水／エタノール混合溶液を調製した。当該混合溶液に、純度９９．５質量％の濃度のアルミニウム基材Ａ１０５０の平板（厚さ０．１ｍｍ、サイズ１００ｍｍ×１００ｍｍ）を浸漬し、実施例１と同様な処理を行った。目視において表面が灰色に変色していることが観測された。走査型電子顕微鏡で表面状態を観測したところ、図４に示すように、微細多孔質体構造は観測されなかった。水酸化ナトリウムは強力なアルカリとしてアルミニウム表面と激しく反応したためと思われる。 “Comparative Example 2” In the case of an aluminum plate (NaOH / EtOH / water system) Sodium hydroxide having a concentration of 1.9% by mass was obtained in the same manner as in Example 1 except that sodium hydroxide was used instead of lithium hydroxide. A / water / ethanol mixed solution was prepared. A flat plate (thickness 0.1 mm, size 100 mm × 100 mm) of an aluminum substrate A1050 having a concentration of 99.5% by mass was immersed in the mixed solution, and the same treatment as in Example 1 was performed. It was observed that the surface was visually changed to gray. When the surface state was observed with a scanning electron microscope, a fine porous body structure was not observed as shown in FIG. It seems that sodium hydroxide reacted violently with the aluminum surface as a strong alkali.
　次いで、アルミニウム系材料を、水酸化リチウムを含む塩基と水と有機溶媒を混合した塩基性混合溶液（特に特定の表面張力を有する塩基性混合溶液）で処理することにより、アルミニウム系材料の表面との濡れ性が改善され、アルミニウム表面と水酸化リチウムの速やかな反応が進行して、表層部の少なくとも一部に酸化被膜とは異なる網目状多孔質構造体が形成され、親水性が著しく向上した親水性部材が得られること、および当該親水性部材に対してさらに親水性処理を施した親水性複合部材についても良好な親水性を維持することを確かめた。 Next, the aluminum-based material is treated with a basic mixed solution (particularly a basic mixed solution having a specific surface tension) in which a base containing lithium hydroxide, water, and an organic solvent are mixed. Improved wettability, and the rapid reaction between the aluminum surface and lithium hydroxide progressed, and a network-like porous structure different from the oxide film was formed on at least a part of the surface layer, and the hydrophilicity was remarkably improved. It was confirmed that a hydrophilic member was obtained and that the hydrophilic composite member obtained by further subjecting the hydrophilic member to hydrophilic treatment maintained good hydrophilicity.
　また、「水酸化リチウムを含む塩基性混合溶液」に「親水性微粒子」を混合してなる溶液または懸濁液を用いてアルミニウム系材料を処理することにより、網目状多孔質構造体が形成される側から親水性微粒子が速やかに担持され、簡単なプロセスにより親水性微粒子がより強固に担持された密着性に優れる親水性部材が得られることを確かめた。 In addition, a reticulated porous structure is formed by treating an aluminum-based material with a solution or suspension obtained by mixing “hydrophilic fine particles” with “basic mixed solution containing lithium hydroxide”. It was confirmed that a hydrophilic member excellent in adhesiveness in which hydrophilic fine particles were quickly supported from the side to be supported and the hydrophilic fine particles were more firmly supported by a simple process was obtained.
以下、実施例７～１４に示す。 Examples 7 to 14 are shown below.
「実施例７」親水性部材：アルミニウム板　
　実施例１の処理後のアルミニウム部材の接触角を測定したところ、水滴は被膜表面を広がり、接触角が測定できない程度に小さくなり（便宜上接触角を０度とする）、被膜が超親水性であることを観察できた。また当該被膜を１Ｌの水中に２昼夜浸漬した後に、再度純水接触角を測定したところ、やはり水滴は被膜表面を広がり、接触角が測定できない程度に小さくなり（便宜上接触角を０度とする）、被膜が超親水性であることを観察できた。 "Example 7" hydrophilic member: aluminum plate
When the contact angle of the aluminum member after the treatment in Example 1 was measured, the water droplet spreads on the surface of the coating and became so small that the contact angle could not be measured (the contact angle was set to 0 degree for convenience), and the coating was superhydrophilic. I was able to observe something. Further, when the coating film was immersed in 1 L of water for 2 days and nights, the contact angle of pure water was measured again. As a result, the water droplets spread over the coating surface and became so small that the contact angle could not be measured (the contact angle was set to 0 degree for convenience). ), It was observed that the coating was superhydrophilic.
「実施例８」親水性部材：　アルミニウム・メッシュ
　実施例４の処理をした後のアルミニウム部材の接触角を測定したところ、水滴は被膜表面を広がり、接触角が測定できない程度に小さくなり（便宜上接触角を０度とする）、被膜が超親水性であることを観察できた。また当該被膜を１Ｌの水中に２昼夜浸漬した後に、再度純水接触角を測定したところ、やはり水滴は被膜表面を広がり、接触角が測定できない程度に小さくなり（便宜上接触角を０度とする）、被膜が超親水性であることを観察できた。 [Example 8] Hydrophilic member: Aluminum mesh When the contact angle of the aluminum member after the treatment of Example 4 was measured, the water droplets spread on the surface of the coating and became so small that the contact angle could not be measured (contact for convenience) It was possible to observe that the coating was superhydrophilic. Further, when the coating film was immersed in 1 L of water for 2 days and nights, the contact angle of pure water was measured again. As a result, the water droplets spread over the coating surface and became so small that the contact angle could not be measured (the contact angle was set to 0 degree for convenience). ), It was observed that the coating was superhydrophilic.
「実施例９」　複合親水性部材　（アルミニウム板／カオリナイト）
　実施例１と同様な方法で得られた網目状多孔質構造体を有する親水性部材（アルミニウム板）を、あらかじめ調合した親水微粒子（カオリナイト）懸濁液に浸漬して下記の手順でアルミニウム系複合親水性部材を製造し、水接触角を測定した。 "Example 9" Composite hydrophilic member (aluminum plate / kaolinite)
A hydrophilic member (aluminum plate) having a network-like porous structure obtained in the same manner as in Example 1 was immersed in a previously prepared suspension of hydrophilic fine particles (kaolinite), and an aluminum-based material was subjected to the following procedure. A composite hydrophilic member was produced and the water contact angle was measured.
　平均粒子０．５μｍのカオリナイト（竹原化学工業株式会社製）を５０ｇ量りとり、純水を１０００ｍｌ加えて、株式会社サンテック製ＵＸ-３００型超音波分散機にて６０分間分散させた。この分散液１０ｍｌに室温で網目状多孔質微細構造を有する親水性部材（アルミニウム・板；５×５ｃｍ）を３分間超音波振動させながら浸漬し、５ｍｍ／ｓｅｃで引き上げた。これを３０分間室温で乾燥させ、１５０℃乾燥機で1時間乾燥させた。アルミニウムの表面にカオリナイトが均一に塗布されており、膜の単位面積あたりの質量は４．１ｇ／ｍ2であった。 50 g of kaolinite having an average particle size of 0.5 μm (manufactured by Takehara Chemical Industry Co., Ltd.) was weighed, 1000 ml of pure water was added, and the mixture was dispersed for 60 minutes with a UX-300 type ultrasonic dispersion machine manufactured by Suntech Co., Ltd. A hydrophilic member (aluminum plate; 5 × 5 cm) having a mesh-like porous microstructure was immersed in 10 ml of this dispersion at room temperature while ultrasonically vibrating for 3 minutes, and pulled up at 5 mm / sec. This was dried at room temperature for 30 minutes, and then dried at 150 ° C. for 1 hour. Kaolinite was uniformly applied on the surface of aluminum, and the mass per unit area of the film was 4.1 g / m 2 .
　純水接触角を測定したところ、滴下直後は、５．９度の接触角であったが、１分以内に水滴は被膜表面を広がり、接触角が測定できない程度に小さくなり（便宜上接触角を０°とする）、被膜が超親水性であることを観察できた。上水で３分間洗浄後に純水接触角を測定したところ、純水接触角は０度で親水性の変化は認められなかった。 When the contact angle of pure water was measured, the contact angle was 5.9 degrees immediately after dropping, but the water droplet spread on the surface of the coating within 1 minute and became so small that the contact angle could not be measured (the contact angle was reduced for convenience). It was observed that the coating was superhydrophilic. When the pure water contact angle was measured after washing with clean water for 3 minutes, the pure water contact angle was 0 ° and no change in hydrophilicity was observed.
「実施例１０」　複合親水性部材（アルミニウム板／コロイダルシリカ）
　実施例１で得られた網目状多孔質構造体を有する親水性部材（アルミニウム板）をあらかじめ調合した親水微粒子（コロイダルシリカ）懸濁液に浸漬して下記の手順でアルミニウム系複合親水性部材を製造し、水接触角を測定した。 "Example 10" Composite hydrophilic member (aluminum plate / colloidal silica)
The hydrophilic composite member (aluminum plate) having the network-like porous structure obtained in Example 1 is immersed in a preliminarily prepared suspension of hydrophilic fine particles (colloidal silica), and the aluminum-based composite hydrophilic member is prepared by the following procedure. Manufactured and measured water contact angle.
　平均粒子０．０５μｍのコロイダルシリカ（日産化学工業株式会社製、商品名、ＩＰＡ-ＳＴ）を１０ｇとり、イソプロパノールを１００ｍｌ加えて、株式会社サンテック製、ＵＸ-３００型超音波分散機にて３分間分散させた。この分散液１００ｍｌに室温で網目状多孔質構造を有する親水性部材（アルミニウム板：５×５ｃｍ）を3分間超音波振動させながら浸漬し、４ｍｍ／ｓｅｃで引き上げた。これを３０分間室温で乾燥させ、１５０℃乾燥機で1時間乾燥させた。走査型電子顕微鏡で観察したところ、図５に示すように、アルミニウムの表面にコロイダルシリカが均一に塗布されていた。膜の単位面積あたりの質量は２．２ｇ／ｍ2であった。 Take 10 g of colloidal silica (trade name, IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) having an average particle size of 0.05 μm, add 100 ml of isopropanol, and use a UX-300 type ultrasonic dispersion machine manufactured by Suntech Co., Ltd. for 3 minutes. Dispersed. A hydrophilic member (aluminum plate: 5 × 5 cm) having a mesh-like porous structure was immersed in 100 ml of this dispersion at room temperature while being ultrasonically vibrated for 3 minutes, and pulled up at 4 mm / sec. This was dried at room temperature for 30 minutes, and then dried at 150 ° C. for 1 hour. When observed with a scanning electron microscope, colloidal silica was uniformly applied to the surface of aluminum as shown in FIG. The mass per unit area of the membrane was 2.2 g / m 2 .
　純水接触角を測定したところ、滴下直後は、５．３度の接触角であったが、１分以内に水滴は被膜表面を広がり、接触角が測定できない程度に小さくなり（便宜上接触角を０度とする）、被膜が超親水性であることを観察できた。上水で３分間洗浄後に純水接触角を測定したところ、純水接触角は０度で親水性の変化は認められなかった。 When the contact angle of pure water was measured, the contact angle was 5.3 degrees immediately after the dropping, but within 1 minute, the water droplet spread on the surface of the coating and became so small that the contact angle could not be measured. It was observed that the coating was superhydrophilic. When the pure water contact angle was measured after washing with clean water for 3 minutes, the pure water contact angle was 0 ° and no change in hydrophilicity was observed.
「実施例１１」　複合親水性部材　（アルミニウム・メッシュ／コロイダルシリカ）　
実施例８と同様な方法で得られた網目状多孔質構造体を有する親水性部材（アルミニウム・メッシュ）をあらかじめ調合した親水微粒子（コロイダルシリカ）懸濁液に浸漬して下記の手順でアルミニウム系複合親水性部材を製造し、水接触角を測定した。 "Example 11" Composite hydrophilic member (aluminum mesh / colloidal silica)
A hydrophilic member (aluminum mesh) having a network-like porous structure obtained in the same manner as in Example 8 was immersed in a preliminarily prepared hydrophilic fine particle (colloidal silica) suspension, and an aluminum-based material was subjected to the following procedure. A composite hydrophilic member was produced and the water contact angle was measured.
　平均粒子０．０５μｍのコロイダルシリカ（日産化学工業株式会社製、商品名ＩＰＡ-ＳＴ）を１０ｇとり、イソプロパノールを１００ｍｌ加えて、株式会社サンテック製、ＵＸ-３００型超音波分散機にて３分間分散させた。この分散液１００ｍｌに室温で、実施例２と同様な方法で得られた網目状多孔質構造を有する親水性部材（アルミニウム・メッシュ）を3分間超音波振動させながら浸漬し、５ｍｍ／ｓｅｃで引き上げた。これを３０分間室温で乾燥させ、１５０℃乾燥機で1時間乾燥させた。走査型電子顕微鏡で観察したところ、アルミニウムの表面にコロイダルシリカが均一に塗布されていた。膜の単位面積あたりの質量は６．３ｇ／ｍ2であった。 Take 10 g of colloidal silica (trade name IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) with an average particle size of 0.05 μm, add 100 ml of isopropanol, and disperse for 3 minutes using a UX-300 type ultrasonic disperser manufactured by Suntech Co., Ltd. I let you. A hydrophilic member (aluminum mesh) having a mesh-like porous structure obtained in the same manner as in Example 2 was immersed in 100 ml of this dispersion at room temperature while being ultrasonically vibrated for 3 minutes and pulled up at 5 mm / sec. It was. This was dried at room temperature for 30 minutes, and then dried at 150 ° C. for 1 hour. When observed with a scanning electron microscope, colloidal silica was uniformly coated on the surface of aluminum. The mass per unit area of the membrane was 6.3 g / m 2 .
　純水接触角を測定したところ、滴下直後は、６．１度の接触角であったが、１分以内に水滴は被膜表面を広がり、接触角が測定できない程度に小さくなり（便宜上接触角を０度とする）、被膜が超親水性であることを観察できた。上水で３分間洗浄後に純水接触角を測定したところ、純水接触角は０度で親水性の変化は認められなかった。 When the contact angle of pure water was measured, the contact angle was 6.1 degrees immediately after dropping, but within 1 minute, the water droplets spread on the surface of the coating and became so small that the contact angle could not be measured. It was observed that the coating was superhydrophilic. When the pure water contact angle was measured after washing with clean water for 3 minutes, the pure water contact angle was 0 ° and no change in hydrophilicity was observed.
「実施例１２」　複合親水性部材　（アルミニウム板／雲母）
　実施例１と同様な方法で得られた網目状多孔質構造を有する親水性部材（アルミニウム板）にあらかじめ調合した親水微粒子（雲母）懸濁液に浸漬して下記の手順でアルミニウム系複合親水性部材を製造した。 "Example 12" Composite hydrophilic member (aluminum plate / mica)
It is immersed in a hydrophilic fine particle (mica) suspension prepared in advance in a hydrophilic member (aluminum plate) having a mesh-like porous structure obtained by the same method as in Example 1, and an aluminum-based composite hydrophilic property is obtained by the following procedure. A member was manufactured.
　平均粒子３μｍの雲母（株式会社ヤマグチマイカ製、商品名、Ａ－１１）を５ｇとり、エタノールを１００ｍｌ加えて、株式会社サンテック製、ＵＸ-３００型超音波分散機にて６０分間分散させた分散液を静置して５分後に上澄み５０ｍｌを分取した。 Dispersion obtained by taking 5 g of mica (trade name, A-11, manufactured by Yamaguchi Mica Co., Ltd.) having an average particle size of 3 μm, adding 100 ml of ethanol, and dispersing for 60 minutes using a UX-300 type ultrasonic disperser manufactured by Suntech Co., Ltd. The liquid was allowed to stand, and after 5 minutes, 50 ml of the supernatant was collected.
　室温で網目状多孔質細構造を有する親水性部材（アルミニウム・板：５×５ｃｍ）を３分間超音波振動させながら上記の分散液に浸漬し、３ｍｍ／secで引き上げた。これを３０分間室温で乾燥させ、１５０℃乾燥機で1時間乾燥させた。アルミニウムの表面に雲母が均一に塗布されており、膜の単位面積あたりの質量は９．３ｇ／ｍ2であった。 A hydrophilic member (aluminum plate: 5 × 5 cm) having a mesh-like porous fine structure at room temperature was immersed in the dispersion while being ultrasonically vibrated for 3 minutes, and pulled up at 3 mm / sec. This was dried at room temperature for 30 minutes, and then dried at 150 ° C. for 1 hour. Mica was uniformly applied to the surface of aluminum, and the mass per unit area of the film was 9.3 g / m 2 .
純水接触角を測定したところ、滴下直後は、５．１度の接触角であったが、１分以内に水滴は被膜表面を広がり、接触角が測定できない程度に小さくなり（便宜上接触角を０度とする）、被膜が超親水性であることを観察できた。上水で３分間洗浄後に純水接触角を測定したところ、純水接触角は０度で親水性の変化は認められなかった。 When the contact angle of pure water was measured, the contact angle was 5.1 degrees immediately after dropping, but within 1 minute, the water droplets spread on the surface of the coating and became so small that the contact angle could not be measured (for convenience, the contact angle was reduced). It was observed that the coating was superhydrophilic. When the pure water contact angle was measured after washing with clean water for 3 minutes, the pure water contact angle was 0 ° and no change in hydrophilicity was observed.
「実施例１３」複合親水性部材　（アルミニウム板／銀粒子／雲母）
　実施例１と同様な方法で得られた網目状多孔質構造を有する親水性部材（アルミニウム・板）をあらかじめ調合した親水微粒子（銀粒子／雲母）懸濁液に浸漬して下記の手順でアルミニウム系複合親水性部材を製造し、純水接触角を測定した。 "Example 13" Composite hydrophilic member (aluminum plate / silver particles / mica)
A hydrophilic member (aluminum plate) having a mesh-like porous structure obtained in the same manner as in Example 1 was immersed in a suspension of previously prepared hydrophilic fine particles (silver particles / mica) and aluminum was obtained by the following procedure. A system composite hydrophilic member was produced, and a pure water contact angle was measured.
　平均粒子０．２μｍの銀粒子（福田金属箔粉工業株式会社製）を２ｇとり、さらに雲母（竹原化学工業株式会社製、商品名ＳＪ－００５）４ｇを加えイソプロパノールを１００ｍｌ加えて、株式会社サンテック製ＵＸ－３００型超音波分散機にて６０分間分散させ、分散液を調製した。室温で網目状多孔質構造を有する親水性部材（アルミニウム・板；５×５ｃｍ）を３分間超音波振動させながら上記の分散液に浸漬し、次いで３ｍｍ／ｓｅｃの速度で引き上げた。これを３０分間室温で乾燥させ、１５０℃乾燥機で１時間乾燥させた。アルミニウムの表面に銀微粒子と雲母が均一に塗布されており、膜の単位面積あたりの質量は３．９ｇ／ｍ2であった。 Take 2g of silver particles with an average particle size of 0.2μm (Fukuda Metal Foil Powder Co., Ltd.), add 4g of mica (Takehara Chemical Co., Ltd., trade name SJ-005) and add 100ml of isopropanol. A dispersion was prepared by dispersing for 60 minutes using a UX-300 type ultrasonic disperser. A hydrophilic member (aluminum plate; 5 × 5 cm) having a mesh-like porous structure at room temperature was immersed in the above dispersion while ultrasonically vibrating for 3 minutes, and then pulled up at a speed of 3 mm / sec. This was dried at room temperature for 30 minutes and then dried at 150 ° C. for 1 hour. Silver fine particles and mica were uniformly applied on the surface of aluminum, and the mass per unit area of the film was 3.9 g / m 2 .
　純水接触角を測定したところ、滴下直後は、５．５度の接触角であったが、１分以内に水滴は被膜表面を広がり、接触角が測定できない程度に小さくなり（便宜上接触角を０度とする）、被膜が超親水性であることを観察できた。上水で３分間洗浄後に純水接触角を測定したところ、純水接触角は０度で親水性の変化は認められなかった。 When the contact angle of pure water was measured, the contact angle was 5.5 degrees immediately after dropping, but within 1 minute the water droplet spread on the surface of the coating and became so small that the contact angle could not be measured. It was observed that the coating was superhydrophilic. When the pure water contact angle was measured after washing with clean water for 3 minutes, the pure water contact angle was 0 ° and no change in hydrophilicity was observed.
「実施例１４」複合親水性部材　（アルミニウム板／ホタテ焼成貝カルシウム）
　実施例１と同様な方法で得られた網目状多孔質構造を有する親水性部材（アルミニウム・板）をあらかじめ調合した親水微粒子（ホタテ焼成貝カルシウム）懸濁液に浸漬して下記の手順でアルミニウム系複合親水性部材を製造し、純水接触角を測定した。 Example 14: Composite hydrophilic member (aluminum plate / scallop calcined shell calcium)
A hydrophilic member (aluminum / plate) having a mesh-like porous structure obtained by the same method as in Example 1 was immersed in a suspension of previously prepared hydrophilic fine particles (scallop calcined calcium shell) and aluminum was obtained in the following procedure. A system composite hydrophilic member was produced, and a pure water contact angle was measured.
　平均直径３μｍのホタテ焼成貝オホーツクカルシウム（日本天然素材製）５ｇをとり、メタノールを１００ｍｌ加えて、ボールミルで３時間粉砕し、分散液を調製した。室温で網目状多孔質構造を有する親水性部材（アルミニウム板）を超音波振動させながら３分間上記の分散液に浸漬し、次いで３ｍｍ／ｓｅｃの速度で引き上げた。これを３０分間室温で乾燥させ、次いで１５０℃乾燥機で1時間乾燥させた。アルミニウム板の表面を目視にて観察したところ、外観は灰色の被膜であり、表面にホタテ焼成貝オホーツクカルシウムが均一に塗布されていた。膜の単位面積あたりの質量は７．０ｇ／ｍ2であった。 5 g of scallop calcined shellfish Okhotsk calcium (manufactured by Japan Natural Materials) having an average diameter of 3 μm was taken, 100 ml of methanol was added, and the mixture was pulverized with a ball mill for 3 hours to prepare a dispersion. A hydrophilic member (aluminum plate) having a reticulated porous structure at room temperature was immersed in the dispersion for 3 minutes while being ultrasonically vibrated, and then pulled up at a speed of 3 mm / sec. This was dried at room temperature for 30 minutes and then dried in a 150 ° C. dryer for 1 hour. When the surface of the aluminum plate was observed with the naked eye, the appearance was a gray film, and the scallop calcined okhotsk calcium was uniformly applied to the surface. The mass per unit area of the membrane was 7.0 g / m 2 .
　純水接触角を測定したところ、滴下直後は、４．９度の接触角であったが、１分以内に水滴は被膜表面を広がり、接触角が測定できない程度に小さくなり（便宜上接触角を０度とする）、被膜が超親水性であることを観察できた。上水で３分間洗浄後に純水接触角を測定したところ、純水接触角は０度で親水性の変化は認められなかった。 When the contact angle of pure water was measured, it was a contact angle of 4.9 degrees immediately after dropping, but within one minute, the water droplet spread on the surface of the coating and became so small that the contact angle could not be measured (the contact angle was reduced for convenience). It was observed that the coating was superhydrophilic. When the pure water contact angle was measured after washing with clean water for 3 minutes, the pure water contact angle was 0 ° and no change in hydrophilicity was observed.
　次いで、「水酸化リチウムを含む塩基性混合溶液」に「親水性微粒子」を混合してなる溶液または懸濁液を用いてアルミニウム系材料を処理することにより、網目状多孔質構造体が形成される側から親水性微粒子が速やかに担持され、簡単なプロセスにより親水性微粒子がより強固に担持された密着性に優れる親水性部材が得られることを確かめた。 Next, the aluminum-based material is processed using a solution or suspension obtained by mixing “hydrophilic fine particles” with “basic mixed solution containing lithium hydroxide” to form a network-like porous structure. It was confirmed that a hydrophilic member excellent in adhesiveness in which hydrophilic fine particles were quickly supported from the side to be supported and the hydrophilic fine particles were more firmly supported by a simple process was obtained.
以下、実施例１５～１７に示す。 Examples 15 to 17 are shown below.
「実施例１５」　親水性部材：アルミニウム板　
　水酸化リチウム一水和物（ＬｉＯＨ・Ｈ2Ｏ：和光特級試薬）を３００ｍｌビーカーに６．０ｇ（０．１４ｍｏｌ）秤り取り、次いでイオン交換水１００ｍｌを加えて常温で攪拌し溶解させた。さらに特級エタノール１００ｍｌを攪拌しながら徐々に添加して、１．９質量％の濃度の水酸化リチウム処理溶液を調製した。当該処理溶液のｐＨは、１１．１であった。 "Example 15" Hydrophilic member: aluminum plate
Lithium hydroxide monohydrate (LiOH.H 2 O: Wako Special Grade Reagent) was weighed out in a 300 ml beaker, 6.0 g (0.14 mol) was added, and then 100 ml of ion-exchanged water was added and stirred at room temperature for dissolution. Further, 100 ml of special grade ethanol was gradually added with stirring to prepare a lithium hydroxide treatment solution having a concentration of 1.9% by mass. The pH of the treatment solution was 11.1.
　上記塩基性混合用液に、親水性微粒子として平均粒子０．５μｍのカオリナイト（竹原化学工業株式会社製）を１０．０ｇ入れ、株式会社サンテック製ＵＸ－３００型超音波分散機にて２０分間分散させ微粒子混合液とした。 10.0 g of kaolinite (manufactured by Takehara Chemical Industry Co., Ltd.) having an average particle size of 0.5 μm as hydrophilic fine particles is added to the above basic mixing solution, and then used for 20 minutes with a UX-300 type ultrasonic disperser manufactured by Suntech Co. A fine particle mixed solution was dispersed.
　この微粒子混合液に、純度９９．５質量％のアルミニウム基材：Ａ１０５０の平板（厚さ０．１ｍｍ、大きさ１００ｍｍ×５０ｍｍ）を室温で超音波振動させながら浸漬した。浸漬後３０秒でアルミニウム基材表面から微細な水素の発泡が観察された。約１分間保持浸漬した後、４ｍｍ／ｓｅｃで引き上げて、次いで３０分間室温で乾燥させ、１５０℃乾燥機で１時間乾燥させた。アルミニウムの表面にカオリナイトが均一に塗布されており、膜の単位面積あたりの質量は４．１ｇ／ｍ2であった。 A flat plate (thickness 0.1 mm, size 100 mm × 50 mm) of an aluminum base material: A1050 having a purity of 99.5% by mass was immersed in this fine particle mixture while being ultrasonically vibrated at room temperature. Fine hydrogen foaming was observed from the surface of the aluminum substrate 30 seconds after the immersion. After dipping for about 1 minute, the film was pulled up at 4 mm / sec, then dried at room temperature for 30 minutes, and dried at 150 ° C. for 1 hour. Kaolinite was uniformly applied on the surface of aluminum, and the mass per unit area of the film was 4.1 g / m 2 .
　純水接触角を測定したところ、滴下直後は、５．９度の接触角であったが、２秒以内に水滴は被膜表面を速やかに広がり、接触角が測定できない程度に小さくなり（便宜上接触角を０度とする）、被膜が超親水性であることを観察できた。さらに上水で３分間十分に表面を洗浄した後に、１００℃で1時間乾燥後、再度純水接触角を測定したところ、純水接触角は０度で親水性の変化は認められなかった。またＳＥＭで表面を観察したところ洗浄前後でも多孔質体や親水性微粒子は十分に担持しており堅牢な被膜であった。 When the contact angle of pure water was measured, it was a contact angle of 5.9 degrees immediately after dropping, but within 2 seconds, the water droplet spread quickly on the surface of the coating and became so small that the contact angle could not be measured (contact for convenience) It was possible to observe that the coating was superhydrophilic. Further, after thoroughly washing the surface with clean water for 3 minutes, drying at 100 ° C. for 1 hour and measuring the pure water contact angle again, the pure water contact angle was 0 ° and no change in hydrophilicity was observed. When the surface was observed with an SEM, the porous body and hydrophilic fine particles were sufficiently supported even before and after washing, and the film was robust.
「実施例１６」
　親水性微粒子としてコロイダルシリカを用いた以外は、実施例１と同様な方法で親水性部材を製造した。 "Example 16"
A hydrophilic member was produced in the same manner as in Example 1 except that colloidal silica was used as the hydrophilic fine particles.
　実施例１５と同様の方法で調製した塩基性混合溶液に、親水性微粒として平均粒子０．０５μｍのコロイダルシリカ（日産化学工業株式会社製、商品名、ＩＰＡ－ＳＴ）を１０ｇとり、株式会社サンテック製ＵＸ－３００型超音波分散機にて２０分間分散させ白乳色の微粒子混合液を調製した。 10 g of colloidal silica (trade name, IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) having an average particle size of 0.05 μm as hydrophilic fine particles was added to a basic mixed solution prepared in the same manner as in Example 15, and Suntech Co., Ltd. The mixture was dispersed with a UX-300 type ultrasonic dispersing machine for 20 minutes to prepare a white milky color fine particle mixture.
　この微粒子混合液に、純度９９．５質量％のアルミニウム基材としてのＡ１０５０の平板（厚さ０．１ｍｍ、サイズ１００ｍｍ×５０ｍｍ）を室温で超音波振動させながら浸漬した。浸漬後３０秒でアルミニウム基材表面から微細な水素の発泡が観察された。約１分間浸漬した後、４ｍｍ／ｓｅｃで引き上げて、次いで３０分間室温で乾燥させ、１５０℃乾燥機で１時間乾燥させた。ＳＥＭ観察によると、アルミニウムの多孔質体の空隙の５０％にコロイダルシリカが充填されていた。従来の２段階工程で処理した方法より４２％担持量が減少したが、親水性はまったく変化がなく、純水接触角も４．５度を示した。１段階工程では親水微粒子の担持量が半減するが、親水処理したアルミニウム基材の後加工において（切断、屈曲加工）、１回工程の方が被膜強度に優れていた。これは凹凸被膜に追従して親水微粒子が付着したためと推定される。 In this fine particle mixture, an A1050 flat plate (thickness 0.1 mm, size 100 mm × 50 mm) as an aluminum substrate having a purity of 99.5% by mass was immersed while being ultrasonically vibrated at room temperature. Fine hydrogen foaming was observed from the surface of the aluminum substrate 30 seconds after the immersion. After being immersed for about 1 minute, it was pulled up at 4 mm / sec, then dried at room temperature for 30 minutes, and dried at 150 ° C. for 1 hour. According to SEM observation, 50% of the voids in the porous aluminum body were filled with colloidal silica. Although the carrying amount decreased by 42% compared to the conventional method treated in the two-step process, the hydrophilicity was not changed at all, and the pure water contact angle was 4.5 degrees. Although the amount of hydrophilic fine particles supported is reduced by half in the one-step process, the post-process (cutting and bending process) of the hydrophilic-treated aluminum substrate was superior in coating strength in the one-time process. This is presumably because the hydrophilic fine particles adhered following the uneven coating.
「実施例１７」
　親水性微粒子として貝殻焼成カルシウムを用いた以外は、実施例１５と同様な方法で親水性部材を製造した。 "Example 17"
A hydrophilic member was produced in the same manner as in Example 15 except that calcined shell calcium was used as the hydrophilic fine particles.
　実施例１５と同様の方法で調製した塩基性混合溶液に、親水性微粒子として平均粒子５μｍの焼成貝カルシウム（日本天然素材株式会社製）を１０ｇとり、０．１質量％の濃度のＰＶＡ溶液を５ｍｌ添加して、株式会社サンテック製ＵＸ－３００型超音波分散機にて２０分間分散させ微粒子混合液を調製した。 In a basic mixed solution prepared in the same manner as in Example 15, 10 g of calcined shell calcium (manufactured by Nippon Natural Materials Co., Ltd.) having an average particle size of 5 μm as hydrophilic fine particles was taken, and a PVA solution having a concentration of 0.1 mass% was taken 5 ml was added and dispersed for 20 minutes with a UX-300 type ultrasonic disperser manufactured by Suntec Co., Ltd. to prepare a fine particle mixture.
　この微粒子混合液に、純度９９．５質量％のアルミニウム基材Ａ１０５０の平板（厚さ０．１ｍｍ、サイズ１００ｍｍ×５０ｍｍ）を室温で超音波振動させながら浸漬した。浸漬後３０秒でアルミニウム基材表面から微細な水素の発泡が観察された。約１分間浸漬した後、４ｍｍ／ｓｅｃで引き上げて、次いで３０分間室温で乾燥させ、１５０℃乾燥機で１時間乾燥させた。ＳＥＭ観察によると、アルミニウムの多孔質体の空隙に一部の微細な焼成貝微粒子が充填され、３μｍ～１０μｍの粗粒子は多孔質体の凹部にアンカー効果で固着しており、純水接触角も８．２度の親水性を示した。基材の後加工において（切断、屈曲加工）も被膜が剥離等が見られず耐久性に優れていた。 A flat plate (thickness 0.1 mm, size 100 mm × 50 mm) of an aluminum base material A1050 having a purity of 99.5% by mass was immersed in this fine particle mixture while being ultrasonically vibrated at room temperature. Fine hydrogen foaming was observed from the surface of the aluminum substrate 30 seconds after the immersion. After being immersed for about 1 minute, it was pulled up at 4 mm / sec, then dried at room temperature for 30 minutes, and dried at 150 ° C. for 1 hour. According to SEM observation, some fine baked shellfish particles are filled in the voids of the porous body of aluminum, and the coarse particles of 3 μm to 10 μm are fixed to the recesses of the porous body by the anchor effect, and the pure water contact angle Also showed a hydrophilicity of 8.2 degrees. Also in the post-processing of the substrate (cutting and bending processing), the coating did not peel off and was excellent in durability.
本発明のアルミニウム系網目状多孔質構造体は、その多孔質が担体として有用であり、その多孔質の中に、触媒、色素、吸着性、親水性、撥水性の機能性を有する微粒子を担持固定化することにより当該機能を有する機能性材料として有用である。例えば、機能性微粒子としての超親水性微粒子を担持固定化させることで、網目状多孔質構造体は超親水性を示す親水性部材となり、ヒートパイプ、フィン等の熱交換素子の部材として有用に活用される。 The aluminum network porous structure of the present invention is useful as a carrier, and supports fine particles having a catalyst, a dye, adsorptivity, hydrophilicity, and water repellency in the porous body. It is useful as a functional material having the function by immobilization. For example, by supporting and fixing superhydrophilic fine particles as functional fine particles, the mesh-like porous structure becomes a hydrophilic member exhibiting superhydrophilic properties, and is useful as a member of heat exchange elements such as heat pipes and fins. Be utilized.

Claims (21)

  1. 母材がアルミニウムもしくはその合金からなり、表層部の少なくとも一部を、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液で処理して形成した網目状多孔質構造体であって、当該網目状多孔質構造が、孔径５ｎｍ～５００ｎｍ、深さ０．０５μｍ～１０μｍの範囲内にある細孔を含むことを特徴とする網目状多孔質構造体。 A network-like porous structure formed by treating the base material with aluminum or an alloy thereof and treating at least a part of the surface layer with a basic mixed solution in which a base containing lithium hydroxide, water and an organic solvent are mixed. A network porous structure, wherein the network porous structure includes pores having a pore diameter of 5 nm to 500 nm and a depth of 0.05 μm to 10 μm.
  2. アルミニウムもしくはその合金を、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液で処理することにより、アルミニウムもしくはその合金の表層部の少なくとも一部に、網目状多孔質の細孔を形成することを特徴とする網目状多孔質構造体の製造方法。 By treating aluminum or an alloy thereof with a basic mixed solution in which a base containing lithium hydroxide, water, and an organic solvent are mixed, at least a part of the surface layer portion of the aluminum or the alloy has a mesh-like porous fine structure. A method for producing a reticulated porous structure, wherein pores are formed.
  3. 塩基性混合溶液を構成する混合溶媒の表面張力が、１８ｍＮ／ｍ～６０ｍＮ／ｍの範囲内であることを特徴とする請求項２に記載のアルミニウム系親水性部材の製造方法。 The method for producing an aluminum-based hydrophilic member according to claim 2, wherein the surface tension of the mixed solvent constituting the basic mixed solution is in the range of 18 mN / m to 60 mN / m.
  4. 塩基性混合溶液中の有機溶媒が、アルコール系、ニトリル系、ケトン系、エステル系、エーテル系、スルホキシド系、アミド系、グリコール系、芳香族系もしくは、含フッ素アルコール系の溶媒の少なくとも一種である請求項２または請求項３に記載の網目状多孔質構造体の製造方法。 The organic solvent in the basic mixed solution is at least one of an alcohol, nitrile, ketone, ester, ether, sulfoxide, amide, glycol, aromatic, or fluorinated alcohol solvent. The manufacturing method of the mesh-shaped porous structure of Claim 2 or Claim 3.
  5. 塩基性混合溶液のｐＨが、９．０～１３．５の範囲内にあることを特徴とする請求項２乃至請求項４のいずれか１項に記載の網目状多孔質構造体の製造方法。 The method for producing a reticulated porous structure according to any one of claims 2 to 4, wherein the pH of the basic mixed solution is in a range of 9.0 to 13.5.
  6. 母材がアルミニウムもしくはその合金からなり、表層部の少なくとも一部を、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液で処理して形成した網目状多孔質構造体を有する親水性部材であって、当該網目状多孔質構造体が、孔径５ｎｍ～５００ｎｍ、深さ０．０５μｍ～１０μｍの範囲内にある細孔を含むことを特徴とする親水性部材。 A mesh-like porous structure formed by treating a base material made of aluminum or an alloy thereof and treating at least a part of a surface layer portion with a basic mixed solution in which a base containing lithium hydroxide, water, and an organic solvent are mixed. A hydrophilic member, characterized in that the network porous structure includes pores having a pore diameter of 5 nm to 500 nm and a depth of 0.05 μm to 10 μm.
  7. 下記、第一工程よりなるアルミニウム系親水性部材の製造方法。
    第一工程：アルミニウムもしくはその合金を、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液で処理することにより、アルミニウムもしくはその合金の表層部の少なくとも一部に、網目状多孔質の細孔を形成する工程。     The manufacturing method of the aluminum-type hydrophilic member which consists of the following and 1st processes.
    First step: By treating aluminum or an alloy thereof with a basic mixed solution in which a base containing lithium hydroxide, water and an organic solvent are mixed, at least a part of the surface layer of aluminum or an alloy thereof has a mesh shape. A step of forming porous pores.
  8. 塩基性混合溶液を構成する混合溶媒の表面張力が、１８ｍＮ／ｍ～６０ｍＮ／ｍの範囲内であることを特徴とする請求項７に記載のアルミニウム系親水性部材の製造方法。 The method for producing an aluminum-based hydrophilic member according to claim 7, wherein the surface tension of the mixed solvent constituting the basic mixed solution is in a range of 18 mN / m to 60 mN / m.
  9. 塩基性混合溶液中の有機溶媒が、アルコール系、ニトリル系、ケトン系、エステル系、エーテル系、スルホキシド系、アミド系、グリコール系、芳香族系もしくは、含フッ素アルコール系の溶媒の少なくとも一種である請求項７または請求項８に記載のアルミニウム系親水性部材の製造方法。 The organic solvent in the basic mixed solution is at least one of an alcohol, nitrile, ketone, ester, ether, sulfoxide, amide, glycol, aromatic, or fluorinated alcohol solvent. The manufacturing method of the aluminum-type hydrophilic member of Claim 7 or Claim 8.
  10. 塩基性混合溶液のｐＨが、９．０～１３．５の範囲内にあることを特徴とする請求項７乃至請求項９のいずれか１項に記載のアルミニウム系親水性部材の製造方法。 10. The method for producing an aluminum-based hydrophilic member according to any one of claims 7 to 9, wherein the pH of the basic mixed solution is in a range of 9.0 to 13.5.
  11. 第一工程で得られた網目状多孔質構造を有する親水性部材の多孔質構造部位を担体として、親水性の微粒子を担持固定せしめる第二工程を施すことを特徴とする請求項７乃至請求項１０のいずれか１項に記載のアルミニウム系複合親水性部材の製造方法。 7. The second step of carrying and fixing hydrophilic fine particles using the porous structure portion of the hydrophilic member having a network porous structure obtained in the first step as a carrier. 10. The method for producing an aluminum based composite hydrophilic member according to any one of 10 above.
  12. 親水性の微粒子がコロイダルシリカ、コロイダルアルミナ、コロイド状のチタニア、ゼオライト、シリカゲル、シリカ、アルミナ、チタニア、炭酸カルシウム、酸化カルシウム、タルク、珪藻土、バーミキュライト、ヒル石、弁柄、貝殻焼成カルシウムの微粒子、または、金、銀、白金、パラジウム、ルテニウム、銅、ニッケル、バナジウム、チタン、インジウム、スズ、タングステンのナノ金属粒子もしくはナノ金属コロイドよりなる群より選ばれる少なくとも一つである請求項１１に記載のアルミニウム系複合親水性部材の製造方法。 Hydrophilic fine particles are colloidal silica, colloidal alumina, colloidal titania, zeolite, silica gel, silica, alumina, titania, calcium carbonate, calcium oxide, talc, diatomaceous earth, vermiculite, vermiculite, petal, shell calcined calcium fine particles, Or at least one selected from the group consisting of nanometal particles or nanometal colloids of gold, silver, platinum, palladium, ruthenium, copper, nickel, vanadium, titanium, indium, tin, and tungsten. A method for producing an aluminum-based composite hydrophilic member.
  13. 第二工程において、親水性微粒子の質量が０．１ｇ／ｍ2～２０ｇ／ｍ2の範囲内になるように担持させることを特徴とする請求項１１または請求項１２に記載のアルミニウム系複合親水性部材の製造方法。 13. The aluminum-based composite hydrophilic according to claim 11 or 12, wherein in the second step, the hydrophilic fine particles are supported so that the mass of the hydrophilic fine particles is within a range of 0.1 g / m 2 to 20 g / m 2. A method for manufacturing a structural member.
  14. 請求項１１乃至請求項１３のいずれか１項に記載の製造方法により製造したアルミニウム系複合親水性部材。 An aluminum-based composite hydrophilic member produced by the production method according to any one of claims 11 to 13.
  15. アルミニウムもしくはその合金を、水酸化リチウムを含む塩基と水と有機溶媒とを混合した塩基性混合溶液に親水性微粒子を混合してなる溶液または懸濁液で処理することにより、アルミニウムもしくはその合金の表層部の少なくとも一部に網目状多孔質構造体を担体として形成するとともに、当該担体に前記親水性微粒子を担持固定させることを特徴とするアルミニウム系親水性部材。 By treating aluminum or an alloy thereof with a solution or suspension obtained by mixing hydrophilic fine particles in a basic mixed solution obtained by mixing a base containing lithium hydroxide, water and an organic solvent, the aluminum or the alloy thereof is treated. An aluminum-based hydrophilic member, wherein a reticulated porous structure is formed on at least a part of a surface layer portion as a carrier, and the hydrophilic fine particles are supported and fixed on the carrier.
  16. 塩基性混合溶液を構成する混合溶媒の表面張力が、１８ｍＮ／ｍ～６０ｍＮ／ｍの範囲内であることを特徴とする請求項１５に記載のアルミニウム系親水性部材。 16. The aluminum-based hydrophilic member according to claim 15, wherein the surface tension of the mixed solvent constituting the basic mixed solution is in the range of 18 mN / m to 60 mN / m.
  17. 塩基性混合溶液中の有機溶媒が、アルコール系、ニトリル系、ケトン系、エステル系、エーテル系、スルホキシド系、アミド系、グリコール系、芳香族系もしくは、含フッ素アルコール系の溶媒の少なくとも一種である請求項１５または請求項１６に記載のアルミニウム系親水性部材。 The organic solvent in the basic mixed solution is at least one of an alcohol, nitrile, ketone, ester, ether, sulfoxide, amide, glycol, aromatic, or fluorinated alcohol solvent. The aluminum-based hydrophilic member according to claim 15 or 16.
  18. 塩基性混合溶液のｐＨが、９．０～１３．５の範囲内にあることを特徴とする請求項１５乃至請求項１７のいずれか１項に記載のアルミニウム系親水性部材。 The aluminum-based hydrophilic member according to any one of claims 15 to 17, wherein the pH of the basic mixed solution is in a range of 9.0 to 13.5.
  19. 網目状多孔質構造体が孔径５ｎｍ～５００ｎｍ、深さ０．０５μｍ～１０μｍの範囲内にある細孔を含むことを特徴とする請求項１５に記載のアルミニウム系親水性部材。 16. The aluminum-based hydrophilic member according to claim 15, wherein the network porous structure includes pores having a pore diameter of 5 nm to 500 nm and a depth of 0.05 μm to 10 μm.
  20. 親水性微粒子がコロイダルシリカ、コロイダルアルミナ、コロイド状のチタニア、ゼオライト、シリカゲル、シリカ、アルミナ、チタニア、炭酸カルシウム、酸化カルシウム、タルク、珪藻土、バーミキュライト、ヒル石、弁柄、貝殻焼成カルシウムの微粒子、または、金、銀、白金、パラジウム、ルテニウム、銅、ニッケル、バナジウム、チタン、インジウム、スズ、タングステンのナノ金属粒子もしくはナノ金属コロイドよりなる群より選ばれる少なくとも一つである請求項１５に記載のアルミニウム系親水性部材。 Hydrophilic fine particles are colloidal silica, colloidal alumina, colloidal titania, zeolite, silica gel, silica, alumina, titania, calcium carbonate, calcium oxide, talc, diatomaceous earth, vermiculite, leechite, petal, shell calcined calcium fine particles, or The aluminum according to claim 15, which is at least one selected from the group consisting of nanometal particles or nanometal colloids of gold, silver, platinum, palladium, ruthenium, copper, nickel, vanadium, titanium, indium, tin, and tungsten. Based hydrophilic member.
  21. 親水性微粒子の質量が０．１ｇ／ｍ2の～２０ｇ／ｍ2の範囲内になるように担持させることを特徴とする請求項１５に記載のアルミニウム系親水性部材。 The aluminum-based hydrophilic member according to claim 15, wherein the hydrophilic fine particles are supported so that the mass of the hydrophilic fine particles is in a range of 0.1 g / m 2 to 20 g / m 2 .
PCT/JP2010/053315 2009-03-02 2010-03-02 Porous network structure, hydrophilic member utilizing same, and processes for producing the porous network structure and the hydrophilic member WO2010101136A1 (en)

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JP2009048613A JP2010202924A (en) 2009-03-02 2009-03-02 Reticulated porous structure and method for producing the same
JP2009048619A JP2010202925A (en) 2009-03-02 2009-03-02 Hydrophilic member and method for producing the same
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