WO2012053497A1 - 金属材用親水性皮膜、親水化処理剤、及び親水化処理方法 - Google Patents
金属材用親水性皮膜、親水化処理剤、及び親水化処理方法 Download PDFInfo
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- WO2012053497A1 WO2012053497A1 PCT/JP2011/073889 JP2011073889W WO2012053497A1 WO 2012053497 A1 WO2012053497 A1 WO 2012053497A1 JP 2011073889 W JP2011073889 W JP 2011073889W WO 2012053497 A1 WO2012053497 A1 WO 2012053497A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
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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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F1/00—Tubular elements; Assemblies of tubular elements
- F28F1/10—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses
- F28F1/12—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element
- F28F1/24—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element and extending transversely
- F28F1/32—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element and extending transversely the means having portions engaging further tubular elements
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/04—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by preventing the formation of continuous films of condensate on heat-exchange surfaces, e.g. by promoting droplet formation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2215/00—Fins
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- the present invention relates to a hydrophilic film formed on the surface of a metal material, a hydrophilic treatment agent for obtaining a hydrophilic film, and a hydrophilic treatment method.
- An air conditioner having functions such as cooling, heating, and dehumidification includes a heat exchanger fin in its heat exchange section.
- the fin material for forming this heat exchanger fin is generally lightweight, excellent in workability, and excellent in thermal conductivity, so that metal materials such as aluminum, aluminum alloy, copper, copper alloy, etc. Formed with.
- Condensation water generated in the heat radiating section and cooling section of the heat exchanger is not quickly removed from the surface of the heat exchanger, but is gradually dried and released into the atmosphere when the air conditioner stops.
- a high humidity state occurs in the heat exchanger section. Due to this high humidity state, bacteria and molds are likely to grow in the heat exchanger, and when these grow, unpleasant odor is felt when the air conditioner is operated, or the metal material forming the heat exchanger is It causes the problem of corrosion.
- molds particularly hygroscopic molds, grow in the heat exchanger section, and these molds are involved in unpleasant odors (Non-Patent Documents 1, 2, and 3).
- Patent Document 1 As a method for imparting hydrophilicity, antibacterial properties, and antifungal properties to the surface of a heat exchanger member, for example, a method using a treatment agent in which polyvinyl alcohol is combined with a specific water-soluble polymer and a crosslinking agent (Patent Document 1). ), A method using a treatment agent in which a specific water-soluble polymer and zinc pyrithione, which is an antibacterial and antifungal component, are combined (Patent Documents 2 and 3), a method using a treatment agent containing antibacterial chitosan (Patent Document 4) ), A method using a treatment agent in which poly (meth) acrylic acid and a specific metal water-soluble compound such as Ce are combined (Patent Document 5) has been proposed.
- the conventional techniques proposed in Patent Documents 1 to 3 above are techniques that can obtain an antifungal effect by separately adding a substance generally called an antibacterial agent. In order not to impair the desired hydrophilicity, there is a limit.
- the conventional technique proposed in Patent Document 4 has a problem that although a film having a low contact angle can be obtained, it is not only impossible to prevent the growth of condensed water, but also antifungal property cannot be obtained.
- an antibacterial component is separately added in addition to the metal water-soluble compound in order to obtain antifungal properties. In this respect, the conventional technique in which the above antibacterial component is added separately. The same problem is concerned.
- the present invention is to solve the above-mentioned problems of the prior art, and its purpose is to provide a hydrophilic film that suppresses the growth of condensed water and imparts antifungal properties to the surface of the metal material, and the like.
- An object of the present invention is to provide a hydrophilic treatment agent and a hydrophilic treatment method for obtaining a hydrophilic film.
- the water contact angle has been measured as a hydrophilicity evaluation method, but the present inventor has found that this evaluation method is not necessarily appropriate. That is, it has been found that a film having a low contact angle cannot always prevent clogging due to condensed water, and only the measurement of the contact angle causes a problem when it is put to practical use.
- the present inventor further indicates that the hydrophilicity necessary for the metal material used in the heat exchanger is not only sufficient for the water contact angle to be low, but the condensed water generated in the actual use environment spreads quickly and uniformly, In other words, it was found that condensation wettability is important, and an evaluation method was established.
- a film capable of suppressing the growth of condensed water can be appropriately evaluated. Based on the establishment of such an evaluation method, the present inventor has completed the present invention as a result of earnest research on a hydrophilic film that suppresses the growth of condensed water and imparts antifungal properties.
- the hydrophilization treatment agent according to the present invention for solving the above-mentioned problems contains water and one or more selected from the poorly water-soluble cerium compound (A) dispersed in the water. It is characterized by doing.
- the hydrophilic film that can be obtained by using the hydrophilizing agent of the present invention can impart excellent condensation wettability and excellent antifungal property to a metal material, and as a result, clogging of condensed water is caused. Problems such as a decrease in heat exchange efficiency and splashing of water droplets can be solved, and further problems such as generation of unpleasant odor due to mold growth and corrosion of metal materials can be solved.
- a preferred embodiment of the hydrophilic treatment agent according to the present invention is configured such that the hardly water-soluble cerium compound (A) is dispersed in the water with a particle size of 0.01 to 2.0 ⁇ m.
- the poorly water-soluble cerium compound (A) is composed of cerium (III) carbonate, cerium fluoride (III), cerium fluoride (IV) and cerium oxide (IV). It comprises so that it may be 1 type, or 2 or more types chosen.
- the preferred embodiment of the hydrophilic treatment agent according to the present invention is further configured to contain one or more selected from the organic component (B) in the water.
- the hydrophilic film according to the present invention for solving the above problems is a hydrophilic film formed on the surface of a metal material, and contains one or more kinds selected from a poorly water-soluble cerium compound (A). It is characterized by doing.
- a preferred embodiment of the hydrophilic film according to the present invention is configured such that the content of the poorly water-soluble cerium compound (A) is 5 to 100% by mass in terms of solid content.
- the poorly water-soluble cerium compound (A) is selected from cerium (III) carbonate, cerium (III) fluoride, cerium (IV) fluoride and cerium (IV) oxide. It comprises so that 1 type or 2 types or more may be contained.
- the preferred embodiment of the hydrophilic film according to the present invention is further configured to contain one or more selected from the organic component (B).
- the hydrophilic film according to the present invention can be obtained by using (1) a hydrophilic treatment agent containing one or more selected from the poorly water-soluble cerium compound (A), (2) the metal material (3) The surface of the metal material that can be obtained by treating the surface with a hydrophilizing agent containing one or more selected from the water-insoluble cerium compound (A) and then drying the surface. Is treated with a hydrophilizing agent containing water and one or more selected from water-insoluble cerium compounds (A) dispersed in the water, and then dried. It can be obtained by a method of forming a hydrophilic film.
- the hydrophilization treatment method according to the present invention for solving the above-mentioned problems is a method in which part or all of the surface of a metal material is selected from water and a poorly water-soluble cerium compound (A) dispersed in the water 1 It is characterized by forming a hydrophilic film after treatment with a hydrophilizing agent containing seeds or two or more kinds.
- membrane is a film
- the metal material according to the present invention for solving the above-described problems is obtained by providing the hydrophilic film according to the present invention on the surface of the metal material.
- a preferable aspect of the metal material according to the present invention is configured such that the metal material is any one selected from an aluminum material, an aluminum alloy material, a copper material, and a copper alloy material. Moreover, it comprises so that the said metal material may be a member of a heat exchanger.
- the hydrophilic film obtained by the hydrophilic treatment agent according to the present invention has excellent dew condensation wettability and excellent antifungal properties. If this hydrophilic film is applied to, for example, aluminum, aluminum alloy, copper, or copper alloy material that constitutes a heat exchanger or the like, problems such as a decrease in heat exchange efficiency due to clogging of condensed water and water droplet scattering are solved. Excellent condensation wettability can be imparted. Moreover, generation
- hydrophilic film The hydrophilic film, the hydrophilic treatment agent and the hydrophilic treatment method according to the present invention will be described in more detail with reference to embodiments.
- the hydrophilic film according to the present invention is a hydrophilic film formed on the surface of a metal material, and is characterized by containing one or more kinds selected from a poorly water-soluble cerium compound (A).
- This hydrophilic film gives excellent condensation wettability and antifungal properties to the metal material.
- the condensation wettability is a method for evaluating the hydrophilicity of a metal material used for a heat exchanger, established by the present inventors. The specific evaluation procedure is as described in the examples described later.
- the metal material used for the heat exchanger has a low water contact angle.
- a metal material having excellent dew condensation wettability is used, it is possible to suppress the growth of dew condensation water generated in an actual use environment and spread it uniformly and quickly.
- the poorly water-soluble cerium compound (A) contained in the hydrophilic film according to the present invention is not particularly limited as long as it is a cerium compound classified as insoluble or hardly soluble in water, and is preferably used. it can.
- cerium (III) carbonate, cerium (III) fluoride, cerium (IV) fluoride, and cerium (IV) oxide in that the condensation wettability and antifungal properties which are the objects of the present invention are excellent.
- two or more of these poorly water-soluble cerium compounds can also be contained. If it further states, it is more preferable to contain cerium (IV) oxide from the viewpoint of highly achieving both the condensation wettability and the antifungal property which are the objects of the present invention.
- cerium (IV) oxide Some of the poorly water-soluble cerium compounds reach cerium (IV) oxide when subjected to external energy such as heat.
- the hydrophilic film is used in order to obtain the condensation wettability and antifungal properties which are the objects of the present invention.
- a part or all of the poorly water-soluble cerium compound contained in may be in the form of cerium (IV) oxide.
- the content of the poorly water-soluble cerium compound (A) contained in the hydrophilic film is preferably 5 to 100% by mass as a solid content ratio with respect to the film quantity of the hydrophilic film.
- the content is 5% by mass or more, the condensation wettability and antifungal properties which are the objects of the present invention are excellent.
- the content of the poorly water-soluble cerium compound (A) is more preferably 30 to 100% by mass as a solid content ratio with respect to the coating amount of the hydrophilic coating.
- the content of the cerium compound (A) is closer to 100% by mass, there is an effect of improving the condensation wettability, which is desirable.
- content of a cerium compound (A) is "100 mass%" it includes the case where the organic component (B) mentioned later is not included at all and the case where it is not included substantially.
- “substantially not contained” means a trace amount that does not exhibit the intrinsic action of the organic component (B), for example, about 0.01 to 1.0% by mass.
- the content (solid content ratio) of the poorly water-soluble cerium compound (A) contained in the hydrophilic film is poorly water-soluble in the hydrophilic treatment agent relative to the total mass excluding water and other volatile components in the hydrophilic treatment agent.
- cerium compound (A) is poorly water-soluble in the hydrophilic treatment agent relative to the total mass excluding water and other volatile components in the hydrophilic treatment agent.
- the coating amount of the hydrophilic coating according to the present invention provided on the surface of the metal material is not particularly limited as long as the condensation wettability and the antifungal properties which are the objects of the present invention are obtained, and can be suitably selected.
- the range of 0.1 to 2.0 g / m 2 is preferable, and the range of 0.1 to 1.0 g / m 2 is more preferable.
- the coating amount is 0.1 g / m 2 or more, the coating of the metal material becomes sufficient, and the condensation wettability that is the object of the present invention becomes more excellent.
- the coating amount is 2.0 g / m 2 or less, the condensation wettability and antifungal properties which are the objects of the present invention can be obtained, and an appropriate coating amount can be obtained.
- the hydrophilic film according to the present invention contains one or more selected from the poorly water-soluble cerium compound (A), it can impart excellent dew condensation wettability and antifungal properties to the metal material.
- improvement of the persistence (water resistance) of the poorly water-soluble cerium compound (A) in water, and the stable water-soluble cerium compound (A) in the hydrophilic treatment agent for obtaining the hydrophilic film according to the present invention For the purpose of dispersing in water, one or more selected from the organic component (B) can be further contained.
- the organic component (B) contained in the hydrophilic film is not particularly limited as long as it does not inhibit the condensation wettability and antifungal properties which are the objects of the present invention.
- Organic acids, surfactants, and polymers Polymers and the like can be suitably used.
- organic acids include oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, malic acid, citric acid, glutamic acid, aspartic acid, tartaric acid, phthalic acid, itaconic acid, melittic acid, trimellitic acid, Trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid, propanedicarboxylic acid, butanedicarboxylic acid, pentanedicarboxylic acid, hexanedicarboxylic acid, heptanedicarboxylic acid, butanetricarboxylic acid, butanetetracarboxylic acid (for example, 1,2,3,4-) Butanetetracarboxylic acid (BTC)), cyclohexanetetracarboxylic acid, hexanetricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 2-phosphonobutane-1,2,2,
- Mintetora methylene phosphonic acid
- Mintetora methylene phosphonic acid
- examples of the cationic counter ion forming the salt include metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions, alkaline earth metal (magnesium, calcium, barium, etc.) ions, ammonium ions, and the like.
- surfactants include polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxypropylene glycol, polyoxyethylene alkyl phenyl ether, glycerin fatty acid partial ester, sorbitan fatty acid partial ester, pentaerythritol fatty acid
- Nonionic (nonionic) surfactants such as partial esters, polyoxyethylene sorbitan acid fatty partial esters, polyoxyethylene alkyl ethers and the like can be mentioned.
- polyoxyethylene alkyl ether carboxylate N-acyl sarcosine, N-acyl glutamate, dialkyl sulfosuccinate, alkane sulfonate, alpha olefin sulfonate, linear alkyl benzene sulfonate, molecular chain Anionic surface activity such as alkylbenzene sulfonate, naphthalene sulfonate-formaldehyde condensate, alkyl naphthalene sulfonate, N-methyl-N-acyl taurine, polyoxyethylene lauryl ether phosphate, polyoxyethylene alkyl ether phosphate Agents.
- Examples of the cationic counter ion that forms these salts include metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions, alkaline earth metal (magnesium, calcium, barium, etc.) ions, ammonium ions, and the like. It is done.
- metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions, alkaline earth metal (magnesium, calcium, barium, etc.) ions, ammonium ions, and the like. It is done.
- cationic surfactants having a quaternary amine such as alkyltrimethylammonium and alkyldimethylbenzylammonium
- amphoteric surfactants such as alkylbetaine, alkylamidopropylbetaine and alkyldimethylamine oxide
- polymer examples include acrylic acid polymer, methacrylic acid polymer, acrylic acid-methacrylic acid copolymer, 2-acrylamido-2-methylpropanesulfonic acid-acrylic acid copolymer, acrylic acid.
- a phosphonic group-containing polymer polyvinyl alcohol, a derivative of polyvinyl alcohol, a cellulose derivative, a starch derivative, a gelatin derivative, a polymer and a copolymer containing 4-styrenesulfonic acid and / or maleic anhydride, Polystyrene-sulfonic acid, vinylsulfonic acid polymer, isoprenesulfonic acid polymer, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinyl Pyridine, acrylamide, Takuriruamido, polymers and copolymers such as
- Examples of the cationic counter ion forming the salt include metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions, alkaline earth metal (magnesium, calcium, barium, etc.) ions, ammonium ions, and the like.
- metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions, alkaline earth metal (magnesium, calcium, barium, etc.) ions, ammonium ions, and the like.
- the content of the organic component (B) in the hydrophilic film is such that (B) :( A) is 0: 100 to 95: 5 as a solid content ratio (mass ratio) with respect to the poorly water-soluble cerium compound (A). Range.
- the organic component (B) is positively contained to improve the persistence (water resistance) of the poorly water-soluble cerium compound (A) in water, and the stable dispersion of the poorly water-soluble cerium compound (A) in the hydrophilic treatment agent.
- (B) :( A) is preferably in the range of 10:90 to 70:30.
- the ratio of (B) is 10 or more, the water resistance and the dispersibility of the poorly water-soluble cerium compound (A) are excellent.
- the ratio of (B) is 70 or less, the condensation wettability and the antifungal property are more excellent.
- organic component (B) those generally classified into nonionic and anionic are preferable.
- organic acids and the surfactants nonionic and anionic surfactants are preferable.
- the polymer polymers include polyvinyl alcohol, polyvinyl alcohol derivatives, nonionic polymer polymers such as polymers and copolymers of N-vinylpyrrolidone, acrylic acid polymers, acrylic acid copolymers, and phosphonic group-containing polymers. Anionic polymer is preferred.
- the hydrophilic film according to the present invention may contain components other than the poorly water-soluble cerium compound (A) and the organic component (B) as long as the object of the present invention is not impaired, but the poorly water-soluble cerium compound.
- the aspect containing only (A) and the aspect containing only a cerium compound (A) and an organic component (B) are preferable.
- the formation method of the hydrophilic film according to the present invention is not particularly limited.
- the hydrophilic film according to the present invention can be obtained by applying the hydrophilic treatment agent according to the present invention to the surface of the metal material and then drying it.
- the hydrophilizing agent according to the present invention used for forming a hydrophilic film having excellent dew condensation wettability and antifungal property is composed of water and a poorly water-soluble cerium compound (A) dispersed in the water. 1 type or 2 types or more selected.
- the poorly water-soluble cerium compound (A) those used in the above-described hydrophilic film according to the present invention can be used.
- the poorly water-soluble cerium compound (A) is one or more selected from cerium carbonate (III), cerium fluoride (III), cerium fluoride (IV) and cerium oxide (IV). Is preferred.
- the 1 type (s) or 2 or more types chosen from an organic component (B) can be contained in the said water.
- an organic component (B) what is used for the hydrophilic membrane
- the hydrophilic treatment agent according to the present invention may contain components other than the poorly water-soluble cerium compound (A) and the organic component (B) in water, as long as the object of the present invention is not impaired.
- An embodiment containing only the poorly water-soluble cerium compound (A) and an embodiment containing only the cerium compound (A) and the organic component (B) are preferred.
- the poorly water-soluble cerium compound (A) is dispersed in the water with a particle diameter in a predetermined range.
- the particle diameter is preferably 0.01 ⁇ m or more.
- the particle diameter is 0.01 ⁇ m or more, since the bonding force between the particles is not so strong when applied to the surface of the metal material, aggregation of the particles is suppressed even after drying, and a uniform film is formed. Therefore, the excellent condensation wettability which is the object of the present invention is obtained.
- the particle diameter is preferably 2.0 ⁇ m or less, and more preferably 1.0 ⁇ m or less. Within the above range, the problem of the hydrophilic film falling off from the metal material hardly occurs, and excellent dew condensation wettability, which is an object of the present invention, is obtained.
- the “particle diameter” refers to a cumulative average diameter (Median diameter) measured by a dynamic light scattering method regardless of primary particles and secondary particles.
- An example of a measuring instrument based on the dynamic light scattering method is UPA-EX150 manufactured by Nikkiso Co., Ltd.
- the measurement principle by the dynamic scattering method is that the weak scattered light from the particle and the reference wave are mixed with the incident light (laser light) (heterodyne method), taken out as an electrical signal by a photodetector, and frequency analysis ( The particle size distribution can be obtained by performing FFT.
- UPA-EX150 a specific measurement method using UPA-EX150 is shown.
- the device specifications of UPA-EX150 are that the light source is a semiconductor laser of 780 nm and 3 mW, and the optical probe is an internal probe system.
- the measurement method is to dilute the hydrophilization treatment agent according to the present invention with deionized water so that the concentration of the poorly water-soluble cerium compound (A) is about 0.01%, and then thoroughly stir and disperse it into the measurement section. And measure.
- the measurement conditions are a measurement time of 180 seconds, no circulation, the particle conditions are transmission of particle permeability, the shape is non-spherical, the refractive index is 1.81 (default setting of the apparatus), and the solvent conditions are solvent. Water and solvent refractive index were set to 1.333.
- the method for controlling the particle diameter of the poorly water-soluble cerium compound (A) is not particularly limited.
- a scale-down method of pulverizing with a ball mill, a jet mill, a sand mill, or the like examples thereof include a method or a redox method, a physical vapor deposition method, a laser evaporation method, and a chemical vapor deposition method in which reaction is performed in a gas phase.
- the method for dispersing the poorly water-soluble cerium compound (A) and the organic component (B) in water is not particularly limited.
- the above-described ball mill, jet mill, sand mill, or the like may be used for dispersion, or a stirrer may be used for dispersion.
- Hydrophilic treatment method A method for forming a hydrophilic treatment film on a metal material or a heat exchanger using the metal material as a member using the hydrophilic treatment agent will be described.
- a part or all of the surface of the metal material is treated with the hydrophilic treatment agent according to the present invention, and then dried to form the hydrophilic film according to the present invention.
- the metal material is preferably cleaned in advance with an alkaline or acidic aqueous cleaning agent, but cleaning may be omitted if cleaning is not required.
- a rust prevention process Well-known chromate, zinc phosphate, titanium type
- membranes a chemical conversion treatment film
- the method of treatment is not particularly limited, and examples thereof include a method of applying with an appropriate application means.
- the application means include a roll coating method, a spray method, and an immersion method.
- Heat drying is not particularly limited as long as the water contained in the hydrophilic film is volatilized, and it is preferably dried in the range of 100 to 250 ° C. for 5 seconds to 120 minutes, more preferably 100 ° C. to 200 ° C.
- the drying temperature is 100 ° C. or higher, the time until water sufficiently evaporates from the film is short, and the working efficiency is excellent.
- the drying temperature is 250 ° C. or lower, the bond of the poorly water-soluble cerium compound (A) does not become so strong, and the water resistance and the condensation wettability are excellent.
- the metal material is not particularly limited, but is preferably an aluminum material, an aluminum alloy material, a copper material, or a copper alloy material used for applications in which hydrophilicity is particularly required.
- An exchanger is preferred.
- the metal material which concerns on this invention is a metal material which provided the said hydrophilic film
- the metal material is preferably any one selected from an aluminum material, an aluminum alloy material, a copper material, and a copper alloy material, and is preferably a member of a heat exchanger.
- FIG. 1 is a schematic cross-sectional view showing an example of the metal material of the present invention.
- the configuration in FIG. 1 is an example, and the present invention is not limited to the illustrated configuration.
- both surfaces of a metal material 1 that is a material to be coated have corrosion-resistant films 2 and 2 ′ provided as necessary.
- a hydrophilic film 3, 3 ′ is provided on the corrosion resistant film 2, 2 ′. Note that the corrosion-resistant coatings 2 and 2 ′ may not be provided, and the hydrophilic coating 3 may be provided only on a required surface (one surface).
- the hydrophilic film according to the present invention has excellent hydrophilicity and antifungal properties.
- dew condensation water Excellent condensation wettability that solves problems such as a decrease in heat exchange efficiency due to clogging and scattering of water droplets can be imparted.
- problems such as generation of unpleasant odor due to mold growth and corrosion of metal materials can be suppressed.
- the hydrophilic film according to the present invention can maintain excellent condensation wettability and antifungal properties even during long-term use.
- a hydrophilic film in which a hydrophilic film is formed on a part or all of the surface, excellent condensation that solves problems such as a decrease in heat exchange efficiency due to clogging of condensed water and scattering of water droplets. Since a hydrophilic film with wettability is formed, it has extremely high practical value when applied to a heat exchanger, and is not only highly adaptable to air conditioner parts but also applicable to a wide range of other uses. Can do.
- the present invention will be specifically described with reference to examples and comparative examples.
- the hydrophilic treatment methods for obtaining the hydrophilic films of Examples 1 to 48 and the hydrophilic films of Comparative Examples 1 to 8 are shown below. However, these examples do not limit the scope of the present invention.
- the particle size was measured by the following method. The same applies to other examples and comparative examples.
- the obtained hydrophilizing agent was diluted with deionized water so that the concentration of the poorly water-soluble cerium compound (A) was about 0.01%, and then well stirred and dispersed. And put it in the measuring section.
- the measurement conditions are a measurement time of 180 seconds, no circulation, the particle conditions are transmission of particle permeability, the shape is non-spherical, the refractive index is 1.81 (default setting of the apparatus), and the solvent conditions are The solvent was water and the solvent refractive index was 1.333.
- cerium (III) carbonate octahydrate high-purity reagent: Kanto Chemical Co., Inc.
- An aqueous dispersion having a particle size of 2.5 ⁇ m was obtained and used as a hydrophilic treatment
- An aqueous dispersion having a particle size of 2.0 ⁇ m was obtained and used as a hydrophilic treatment
- An aqueous dispersion having a particle size of 1.0 ⁇ m was obtained and used as a hydrophilic
- An aqueous dispersion having a particle size of 0.5 ⁇ m was obtained and used as a hydrophil
- An aqueous dispersion having a particle size of 0.1 ⁇ m was obtained and used as a hydrophilic
- PVS Physical Vapor Synthesis
- An aqueous dispersion having a diameter of 0.02 ⁇ m was obtained and used as a hydrophilic treatment agent. After dipping and applying the metal material in the hydrophilizing agent, the electric furnace was hung in a blow dryer adjusted to 160 ° C. and heat-dried for 10 minutes. The coating amount on the test material was 0.5 g / m as dry solid content. A hydrophilic film of m 2 was formed.
- PVS Physical Vapor Synthesis
- PVS Physical Vapor Synthesis
- An aqueous dispersion having a diameter of 0.02 ⁇ m was obtained and used as a hydrophilic treatment agent. After immersing and applying the metal material in the hydrophilizing agent, the electric furnace was hung in a blow dryer adjusted to 160 ° C. and heat-dried for 10 minutes. The coating amount on the test material was 0.1 g / kg as a dry solid content. A hydrophilic film of m 2 was formed.
- PVS Physical Vapor Synthesis
- An aqueous dispersion having a diameter of 0.02 ⁇ m was obtained and used as a hydrophilic treatment agent. After dipping and applying the metal material in the hydrophilizing agent, the electric furnace was hung in an air dryer adjusted to 160 ° C. and dried by heating for 10 minutes. The coating amount on the test material was 0.3 g / m as dry solid content. A hydrophilic film of m 2 was formed.
- PVS Physical Vapor Synthesis
- An aqueous dispersion having a diameter of 0.02 ⁇ m was obtained and used as a hydrophilic treatment agent. After immersing and applying the metal material in the hydrophilizing agent, the electric furnace was hung in a blow dryer adjusted to 160 ° C. and dried by heating for 10 minutes. The coating amount on the test material was 2.0 g / m as dry solid content. A hydrophilic film of m 2 was formed.
- aqueous dispersion of cerium (IV) oxide / total amount 3.0 g / 100 g produced by the same method as in Example 18.
- aqueous dispersion of cerium (IV) oxide / total amount 3.0 g / 100 g produced by the same method as in Example 18.
- aqueous dispersion of cerium (IV) oxide / total amount 3.0 g / 100 g produced by the same method as in Example 18. 70 g of an aqueous solution dissolved in water so as to be 3.0
- aqueous dispersion of cerium (IV) oxide / total amount 3.0 g / 100 g prepared by the same method as in Example 18. 10 g of an aqueous solution dissolved in water so as to be 3.0 g
- aqueous dispersion of cerium (IV) oxide / total amount 3.0 g / 100 g produced by the same method as in Example 14. 70 g of an aqueous solution dissolved in water so as to be 3.0
- aqueous dispersion of cerium (IV) oxide / total amount 3.0 g / 100 g produced by the same method as in Example 15. 70 g of an aqueous solution dissolved in water so as to be 3.0 g
- aqueous dispersion of cerium (IV) oxide / total amount 3.0 g / 100 g produced by the same method as in Example 19. 70 g of an aqueous solution dissolved in water so as to be 3.0
- Example 36 After immersing and applying the test material to the hydrophilization treatment agent produced in the same manner as in Example 31, the electric furnace was hung in a blow dryer adjusted to 100 ° C. and dried by heating for 10 minutes, and the film was coated on the test material. A hydrophilic film having a dry solid content of 0.5 g / m 2 was formed.
- Example 37 After immersing and applying the test material to the hydrophilization treatment agent produced by the same method as in Example 31, it was hung in an air dryer adjusted to 200 ° C. in an electric furnace and dried by heating for 10 minutes. Formed a hydrophilic film having a dry solid content of 0.5 g / m 2 .
- polyvinyl alcohol GOHSENOL NM-11: Nippon Synthetic Chemical Industry Co., Ltd.
- the electric furnace After immersing the test material in the hydrophilizing agent and applying it, the electric furnace was hung in a blow dryer adjusted to 160 ° C. and heat-dried for 10 minutes. The coating amount on the test material was 0.5 g / m as dry solid content. A hydrophilic film of m 2 was formed.
- Example 48 2.
- an aqueous dispersion of cerium (IV) oxide / total amount 3.0 g / 100 g prepared by the same method as in Example 18, polyvinyl pyrrolidone (PVP K30: IS Japan Co., Ltd.) as a solid content concentration; 10 g of an aqueous solution dissolved in water so as to be 0 g / 100 g was added to obtain a hydrophilic treatment agent.
- the electric furnace was hung in a blow dryer adjusted to 160 ° C. and heat-dried for 10 minutes.
- the coating amount on the test material was 0.5 g / m as dry solid content.
- a hydrophilic film of m 2 was formed.
- polyvinyl alcohol Gosenol NM-11: Nippon Synthetic Chemical Industry Co., Ltd.
- ⁇ Comparative Example 7> Dissolve 1.5 g of chitosan (Chitosan VL: Dainichi Seika Kogyo Co., Ltd.) and 1.5 g of 1,2,3,4-butanetetracarboxylic acid (Ricacid BT-W: Shin Nippon Rika Co., Ltd.) in water to make the total amount. 100 g of the aqueous solution was used as a hydrophilic treatment agent. After immersing the test material in the hydrophilizing agent and applying it, the electric furnace was hung in a blow dryer adjusted to 160 ° C. and heat-dried for 10 minutes. The coating amount on the test material was 0.5 g / m as dry solid content. A hydrophilic film of m 2 was formed.
- ⁇ Comparative Example 8> An aqueous solution in which 10.0 g of cerium (III) chloride (high purity reagent: Kanto Chemical Co., Inc.) and 5 g of hydrogen peroxide (35% reagent: Wako Pure Chemical Industries, Ltd.) were added to water to make a total amount of 1 L was used as a chemical conversion treatment solution. .
- the chemical conversion solution is heated to 45 ° C, the test material is immersed for 30 minutes, washed with water, hung in an air dryer adjusted to 100 ° C for 10 minutes, and dried for 10 minutes.
- a chemical conversion film having a Ce adhesion amount of 0.1 g / m 2 was formed.
- Tables 1 and 2 show the conditions of Examples 1 to 48, and Table 3 shows the conditions of Comparative Examples 1 to 8.
- “wt%” is synonymous with “mass%”.
- Test materials used in Examples 1 to 27, 29 to 48, and Comparative Examples 1 to 8 were aluminum alloy materials having a thickness of 0.8 mm, a width of 70 mm, and a length of 150 mm, equivalent to a commercial product JIS A 1000.
- the test material used in Example 28 was a commercially available JIS C 1000 equivalent copper alloy material having a thickness of 0.8 mm, a width of 70 mm, and a length of 150 mm.
- test material was treated by adjusting the alkaline degreasing agent “Fine Cleaner 315” (manufactured by Nihon Parkerizing Co., Ltd.) to a chemical concentration of 20 g / L and a bath temperature of 60 ° C. After immersion in a bath for 2 minutes to remove dust and oil adhering to the surface, the alkali remaining on the surface was washed with tap water and used.
- the alkaline degreasing agent “Fine Cleaner 315” manufactured by Nihon Parkerizing Co., Ltd.
- the film performance was evaluated by the following evaluation method.
- ⁇ Antifungal evaluation> After immersing the evaluation material in deionized water for 480 hours, a 40 mm ⁇ 40 mm size test piece was cut out from what was dried by heating in an air dryer adjusted to 50 ° C. for 1 hour and allowed to cool to room temperature. It was. The test specimen is sprayed with a mixed spore suspension of the following 4 species as test bacteria, covered, and cultured for 7 days at 27 ° C. And evaluated with the following rating numbers (based on JIS-Z-2911-2000).
- ⁇ Contact angle with water> The material to be evaluated was immersed in deionized water for 480 hours, then heated and dried for 1 hour in a blast dryer adjusted to 50 ° C. and allowed to cool to room temperature. 2 ⁇ l of deionized water is dropped on the evaluation material, and the contact angle of the formed water droplet is measured with a contact angle meter (trade name: CA-X type, manufactured by Kyowa Interface Science Co., Ltd.). And evaluated.
- Film remaining ratio is 90% or more 4: Film remaining ratio is 70% or more and less than 90% 3: Film remaining ratio is 60% or more and less than 80% 2: Film remaining ratio exceeds 0% and less than 60% 1: Film remaining Rate is 0%
- Ce residual ratio (B) / (A) ⁇ 100 (%)
- Ce residual ratio is 90% or more 4: Ce residual ratio is 80% or more and less than 90% 3: Ce residual ratio is 60% or more and less than 80% 2: Ce residual ratio is more than 0% and less than 60% 1: Ce residual Rate is 0%
- Comparative Examples 1 and 2 are films obtained from a hydrophilizing agent obtained by dissolving a water-soluble cerium compound in water, but water resistance was not obtained. This shows that it is important to use a poorly water-soluble cerium compound.
- Comparative Example 3 is a film of only polyvinyl alcohol, and although the contact angle with water is generally at a level considered to be hydrophilic, it can be seen that the condensation wettability and antifungal properties which are the objects of the present invention cannot be obtained.
- Comparative Example 4 shows a case where an organic component is combined with a water-soluble cerium compound. Although the water resistance (film residual property) and Ce residual property are improved as compared with Comparative Examples 1 and 2, the condensation wettability and It turns out that moldability is not obtained.
- Comparative Examples 5 and 6 show the case where ZPT and ZnO, which are generally known to have antifungal properties, are combined with PVA. In addition to the fact that these films do not provide condensation wettability, both are immersed in deionized water. It can be seen that the residual Zn afterwards is low and antifungal properties cannot be obtained. Comparative Example 7 shows a case where chitosan generally known to have antibacterial properties is used. In addition to the fact that condensation wettability cannot be obtained with this film, antifungal property is seen despite good water resistance. Absent. That is, it can be seen that chitosan has no antifungal property.
- Comparative Example 8 is a case where a chemical conversion film was obtained by a chemical conversion treatment of a Ce compound, and although this film has a high Ce residual property, the condensation wettability and antifungal properties which are the objects of the present invention cannot be obtained. I understand.
- FIG. 2 is a graph showing the relationship between the result of “contact angle (after deionized water immersion)”, which is a general hydrophilicity evaluation method, and the result of “condensation wettability” used as an evaluation method in Examples. is there.
- the plot in FIG. 2 shows the correlation between the contact angle (horizontal axis, raw data) and condensation wettability (vertical axis, rating number) of various coatings including Examples 1 to 48 and Comparative Examples 3 to 8.
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Abstract
Description
本発明者は、さらに、熱交換器に用いる金属材に必要な親水性とは、対水接触角が低いだけでは十分でなく、実使用環境において発生する結露水が均一にすばやく濡れ広がること、すなわち、結露濡れ性が重要となることを見出し、その評価方法を確立した。本発明者が確立した結露濡れ性の評価方法を用いることにより、結露水の成長を抑制しうる皮膜を適切に評価することができるようになった。
本発明者は、このような評価方法の確立に基づき、結露水の成長を抑制し、かつ、抗カビ性を付与する親水性皮膜について鋭意研究した結果、本発明を完成した。
本発明に係る親水性皮膜は、金属材の表面に形成された親水性皮膜であって、水難溶性のセリウム化合物(A)から選ばれる1種又は2種以上を含有することを特徴とする。この親水性皮膜は、金属材に対して優れた結露濡れ性及び抗カビ性を与える。ここで、結露濡れ性とは、本発明者が確立した、熱交換器に供する金属材の親水性の評価方法である。具体的な評価手順は、後述する実施例に記載のとおりである。
本発明に係る親水性皮膜が含有する水難溶性のセリウム化合物(A)は、水に対して不溶又は難溶と分類されるセリウム化合物であれば特に限定されるものではなく、好適に用いることができる。
本発明に係る親水性皮膜は、前記水難溶性のセリウム化合物(A)から選ばれる1種又は2種以上含有することで、優れた結露濡れ性及び抗カビ性を金属材に付与できる。また、水難溶性のセリウム化合物(A)の水に対する残存性(耐水性)の向上、本発明に係る親水性皮膜を得るための親水化処理剤中において水難溶性のセリウム化合物(A)を安定に水の中に分散する目的で、有機成分(B)から選ばれる1種又は2種以上をさらに含有させることができる。
以下、親水性皮膜を得るための親水化処理剤及び親水化処理方法について説明する。
また、前記水の中に、有機成分(B)から選ばれる1種又は2種以上を含有させることができる。有機成分(B)としては、上述した本発明に係る親水性皮膜に用いられるものを用いることができる。
本発明に係る親水化処理剤は、本発明の目的を損なわない範囲で、水の中に、水難溶性のセリウム化合物(A)及び有機成分(B)以外の成分を含んでいてもよいが、水難溶性のセリウム化合物(A)のみを含有する態様、セリウム化合物(A)及び有機成分(B)のみを含有する態様が好ましい。
前記親水化処理剤を用いて、金属材や金属材を部材とした熱交換器に親水性処理皮膜を形成する方法について説明する。本発明に係る親水化処理方法は、金属材の表面の一部又は全部を、上記本発明に係る親水化処理剤で処理した後、乾燥して上記本発明に係る親水性皮膜を形成する。
本発明に係る金属材は、表面に上記親水性皮膜を設けた金属材である。金属材は、アルミニウム材、アルミニウム合金材、銅材及び銅合金材から選ばれる何れかであるのが好ましく、また、熱交換器の部材であるのが好ましい。
炭酸セリウム(III)・8水和物(高純度試薬:関東化学株式会社)に、炭酸セリウム(III)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、炭酸セリウム(III)の粒子径が2.0μmの水分散液を得て、親水化処理剤とした。次いで、親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
炭酸セリウム(III)・8水和物(高純度試薬:関東化学株式会社)に、炭酸セリウム(III)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、炭酸セリウム(III)の粒子径が1.0μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
炭酸セリウム(III)・8水和物(高純度試薬:関東化学株式会社)に、炭酸セリウム(III)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、炭酸セリウム(III)の粒子径が0.5μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
炭酸セリウム(III)・8水和物(高純度試薬:関東化学株式会社)に、炭酸セリウム(III)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、炭酸セリウム(III)の粒子径が0.1μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
フッ化セリウム(III)(試薬:和光純薬工業株式会社)に、フッ化セリウム(III)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、フッ化セリウム(III)の粒子径2.0μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
フッ化セリウム(III)(試薬:和光純薬工業株式会社)に、フッ化セリウム(III)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、フッ化セリウム(III)の粒子径1.0μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
フッ化セリウム(III)(試薬:和光純薬工業株式会社)に、フッ化セリウム(III)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、フッ化セリウム(III)の粒子径0.5μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
フッ化セリウム(III)(試薬:和光純薬工業株式会社)に、フッ化セリウム(III)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、フッ化セリウム(III)の粒子径0.1μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
フッ化セリウム(IV)(試薬:和光純薬工業株式会社)に、フッ化セリウム(IV)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、フッ化セリウム(IV)の粒子径2.0μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
フッ化セリウム(IV)(試薬:和光純薬工業株式会社)に、フッ化セリウム(IV)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、フッ化セリウム(IV)の粒子径1.0μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
フッ化セリウム(IV)(試薬:和光純薬工業株式会社)に、フッ化セリウム(IV)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、フッ化セリウム(IV)の粒子径0.5μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
フッ化セリウム(IV)(試薬:和光純薬工業株式会社)に、フッ化セリウム(IV)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、フッ化セリウム(IV)の粒子径0.1μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
酸化セリウム(IV)(試薬:和光純薬工業株式会社)に、酸化セリウム(IV)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、酸化セリウム(IV)の粒子径2.5μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
酸化セリウム(IV)(試薬:和光純薬工業株式会社)に、酸化セリウム(IV)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、酸化セリウム(IV)の粒子径2.0μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
酸化セリウム(IV)(試薬:和光純薬工業株式会社)に、酸化セリウム(IV)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、酸化セリウム(IV)の粒子径1.0μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
酸化セリウム(IV)(試薬:和光純薬工業株式会社)に、酸化セリウム(IV)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、酸化セリウム(IV)の粒子径0.5μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
酸化セリウム(IV)(試薬:和光純薬工業株式会社)に、酸化セリウム(IV)/全量=3.0g/100gとなるよう水を加えた後、サンドミルにて粉砕し、酸化セリウム(IV)の粒子径0.1μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
Physical Vapor Synthesis(PVS)法により製造された一般に市販される酸化セリウム(IV)微粒子を、酸化セリウム(IV)/全量=3.0g/100gとなるよう水を加え、酸化セリウム(IV)の粒子径0.02μmの水分散液を得て、親水化処理剤とした。親水化処理剤に金属材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
Physical Vapor Synthesis(PVS)法により製造された一般に市販される酸化セリウム(IV)微粒子を、酸化セリウム(IV)/全量=3.0g/100gとなるよう水を加えた後、超音波を当て、酸化セリウム(IV)の粒子径0.01μmの水分散液を得て、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例17と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液50gに、実施例8と同様の方法で作製したフッ化セリウム(III)/全量=3.0g/100gの水分散液50gを加えて親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
Physical Vapor Synthesis(PVS)法により製造された一般に市販される酸化セリウム(IV)微粒子を、酸化セリウム(IV)/全量=1.0g/100gとなるよう水を加え、酸化セリウム(IV)の粒子径0.02μmの水分散液を得て、親水化処理剤とした。親水化処理剤に金属材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.1g/m2の親水性皮膜を形成した。
Physical Vapor Synthesis(PVS)法により製造された一般に市販される酸化セリウム(IV)微粒子を、酸化セリウム(IV)/全量=2.0g/100gとなるよう水を加え、酸化セリウム(IV)の粒子径0.02μmの水分散液を得て、親水化処理剤とした。親水化処理剤に金属材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.3g/m2の親水性皮膜を形成した。
Physical Vapor Synthesis(PVS)法により製造された一般に市販される酸化セリウム(IV)微粒子を、酸化セリウム(IV)/全量=5.0g/100gとなるよう水を加え、酸化セリウム(IV)の粒子径0.02μmの水分散液を得て、親水化処理剤とした。親水化処理剤に金属材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として1.0g/m2の親水性皮膜を形成した。
Physical Vapor Synthesis(PVS)法により製造された一般に市販される酸化セリウム(IV)微粒子を、酸化セリウム(IV)/全量=10.0g/100gとなるよう水を加え、酸化セリウム(IV)の粒子径0.02μmの水分散液を得て、親水化処理剤とした。親水化処理剤に金属材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として2.0g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液を親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を100℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液を親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉200℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液を親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉250℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液を親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液5gに、ポリビニルアルコール(ゴーセノールNM-11:日本合成化学工業株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液95gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液20gに、ポリビニルアルコール(ゴーセノールNM-11:日本合成化学工業株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液80gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液30gに、ポリビニルアルコール(ゴーセノールNM-11:日本合成化学工業株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液70gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液90gに、ポリビニルアルコール(ゴーセノールNM-11:日本合成化学工業株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液10gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例14と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液30gに、ポリビニルアルコール(ゴーセノールNM-11:日本合成化学工業株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液70gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例15と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液30gに、ポリビニルアルコール(ゴーセノールNM-11:日本合成化学工業株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液70gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例19と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液30gに、ポリビニルアルコール(ゴーセノールNM-11:日本合成化学工業株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液70gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例31と同様の方法で作製した親水化処理剤に試験材を浸漬して塗布した後、電気炉を100℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例31と同様の方法で作製した親水化処理剤に試験材を浸漬して塗布した後、電気炉200℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液90gに、ポリアクリル酸(ジュリマーAC-10L:東亞合成株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液10gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液30gに、ポリアクリル酸(ジュリマーAC-10L:東亞合成株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液70gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液20gに、ポリアクリル酸(ジュリマーAC-10L:東亞合成株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液80gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液30gに、ポリアクリル酸(ジュリマーAC-10L:東亞合成株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液35gと、ポリビニルアルコール(ゴーセノールNM-11:日本合成化学工業株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液35gとを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液90gに、2-ホスホノブタン-1,2,4-トリカルボン酸(キレストPH-430:キレスト株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液10gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液90gに、1,2,3,4-ブタンテトラカルボン酸(リカシッドBT-W:新日本理化株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液10gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液90gに、アニオン性界面活性剤であるアルキルフェニルエーテルジスルホン酸Na(ペレックスSS-H:花王株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液10gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液90gに、ノニオン性界面活性剤であるポリオキシアルキレンアルキルエーテル(ノイゲンET-116C:第一工業製薬株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液10gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液90gに、スルホン酸基含有ポリアクリル酸(アロン-A6021:東亞合成株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液10gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液90gに、ポリアクリルアミド(シャロールAM-253P:第一工業製薬株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液10gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
実施例18と同様の方法で作製した酸化セリウム(IV)/全量=3.0g/100gの水分散液90gに、ポリビニルピロリドン(PVP K30:アイエスピー・ジャパン株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液10gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
硝酸セリウム(III)・6水和物(高純度試薬:関東化学株式会社)に、硝酸セリウム(III)/全量=3.0g/100gとなるよう水を加えて溶解し親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
塩化セリウム(III)(高純度試薬:関東化学株式会社)に、塩化セリウム(III)/全量=3.0g/100gとなるよう水を加えて溶解し親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
ポリビニルアルコール(ゴーセノールNM-11:日本合成化学工業株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液を親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
比較例1と同様の方法で作製した硝酸セリウム(III)/全量=3.0g/100gの水溶液30gに、ポリビニルアルコール(ゴーセノールNM-11:日本合成化学工業株式会社)を固形分濃度として3.0g/100となるよう水に溶解した水溶液70gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
ポリビニルアルコール(ゴーセノールNM-11:日本合成化学工業株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液95gに、2-ピリジンギオール-1-オキサイド亜鉛塩(ホクサイドZPT:北興産業株式会社)の固形分濃度が3.0g/100gとなるよう水に分散した水分散液5gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
ポリビニルアルコール(ゴーセノールNM-11:日本合成化学工業株式会社)を固形分濃度として3.0g/100gとなるよう水に溶解した水溶液95gに、酸化亜鉛(NANOBYK-3820:ビックケミージャパン)の固形分濃度が3.0g/100gとなるよう水に分散した水分散液5gを加え、親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
キトサン(キトサンVL:大日精化工業株式会社)1.5gと1,2,3,4-ブタンテトラカルボン酸(リカシッドBT-W:新日本理化株式会社)1.5gを水に溶解し全量を100gとした水溶液を親水化処理剤とした。親水化処理剤に試験材を浸漬して塗布した後、電気炉を160℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量が乾燥固形分として0.5g/m2の親水性皮膜を形成した。
塩化セリウム(III)(高純度試薬:関東化学株式会社)10.0g、過酸化水素(35%試薬:和光純薬工業株式会社)5gを水に加え総量1Lとした水溶液を化成処理液とした。化成処理液を45℃に加温し、試験材を30分間浸漬した後、水洗し、電気炉を100℃に調整した送風乾燥機内で吊るして10分間加熱乾燥し、試験材上に皮膜量がCe付着量として0.1g/m2の化成皮膜を形成した。
実施例1~27、29~48及び比較例1~8に用いた試験材は、市販品のJIS A 1000相当の、厚さ0.8mm、幅70mm、長さ150mmのアルミニウム合金材であった。実施例28に用いた試験材は、市販のJIS C 1000相当の厚さ0.8mm、幅70mm、長さ150mmの銅合金材であった。
前記実施例及び比較例の皮膜を設けるに当たり、前記の試験材を、アルカリ系脱脂剤「ファインクリーナー315」(日本パーカライジング株式会社製)を薬剤濃度:20g/L、浴温度60℃に調整した処理浴に2分間浸漬処理し、表面に付着しているゴミや油を除去した後、表面に残存しているアルカリ分を水道水により洗浄し用いた。
評価材を脱イオン水に480時間浸漬させた後、50℃に調整した送風乾燥器内で1時間加熱乾燥し室温まで放冷したものから、40mm×40mmサイズの試験片を切り出し、評価に用いた。温度25℃、湿度60%RHに調整した雰囲気の中で、試験片を5℃に冷却し5分間冷却した後の試験片表面の結露水の状態を目視にて観察し、表4に示すレイティングナンバーにて評価した。
評価材を脱イオン水に480時間浸漬させた後、50℃に調整した送風乾燥器内で1時間加熱乾燥し室温まで放冷したものから、40mm×40mmサイズの試験片を切り出し、評価に用いた。試験片に対して試験菌として下記の4菌種の混合胞子懸濁液を噴霧し、蓋をして27℃で7日間培養した後のカビの繁殖状態を、試験片面積におけるカビの占有面積により測定し、下記に示すレイティングナンバーにて評価した(JIS-Z-2911-2000に準拠)。
・Aspergillus niger(IFO6341)
・Penicillium funiclosum(IFO6345)
・Cladosporium cladosporioides(IFO6348)
・Aureobasidium pullulans(IFO6353)
5:占有面積1%未満
4:占有面積1%以上10%未満
3:占有面積10%以上30%未満
2:占有面積30%以上60%未満
1:占有面積60%以上
評価材を脱イオン水に480時間浸漬させた後、50℃に調整した送風乾燥器内で1時間加熱乾燥し室温まで放冷したものを評価に用いた。評価材上に2μlの脱イオン水を滴下し、形成された水滴の接触角を接触角計(商品名:CA-X型、協和界面科学株式会社製)により測定し、下記に示すレイティングナンバーにて評価した。
5:接触角が10°未満
4:接触角が10°以上20°未満
3:接触角が20°以上30°未満
2:接触角が30°以上40°未満
1:接触角が40°以上
評価材を脱イオン水に480時間浸漬する前後の質量測定を行い、下記に示す式により皮膜残存率を求め、下記に示すレイティングナンバーにて耐水性を評価した。
A:皮膜を設ける前の試験材質量(g)
B:皮膜を設けた後の評価材質量(g)
C:評価材を脱イオン水中に480時間浸漬した後、乾燥した評価材質量(g)
なお、乾燥した評価材とは、50℃に調整した送風乾燥器内で1時間加熱乾燥し室温まで放冷したものを指す。
5:皮膜残存率が90%以上
4:皮膜残存率が70%以上90%未満
3:皮膜残存率が60%以上80%未満
2:皮膜残存率が0%を超え60%未満
1:皮膜残存率が0%
評価材を脱イオン水に480時間浸漬する前後のCe量を、蛍光X線分析装置(商品名ZSX-100:株式会社リガク製)を用いて測定を行い、下記に示す式によりCe残存率を求め、下記に示すレイティングナンバーにて耐水性を評価した。なお、比較例5、6については、同様の方法により、Zn残存率を求めて耐水性を評価した。比較例3、7については、この評価試験は行わなかった。
A:脱イオン水浸漬前のCe量(mg/m2)
B:脱イオン水に480時間浸漬した後のCe量(mg/m2)
5:Ce残存率が90%以上
4:Ce残存率が80%以上90%未満
3:Ce残存率が60%以上80%未満
2:Ce残存率が0%を超え60%未満
1:Ce残存率が0%
次に、接触角と結露濡れ性について説明する。図2は、一般的な親水性評価方法である「接触角(脱イオン水浸漬後)」の結果と、実施例で評価方法として用いた「結露濡れ性」の結果との関係を示すグラフである。図2中のプロットは、実施例1~48及び比較例3~8を含む各種皮膜の接触角(横軸、生データ)と結露濡れ性(縦軸、レイティングナンバー)との相関を示す。
2,2’ 耐食皮膜(耐食皮膜は無くても良い)
3,3’ 親水性皮膜
10 親水性皮膜が設けられた金属材
Claims (13)
- 水と、該水の中に分散された水難溶性のセリウム化合物(A)から選ばれる1種又は2種以上とを含有することを特徴とする親水化処理剤。
- 前記水難溶性のセリウム化合物(A)が、0.01~2.0μmの粒子径で前記水の中に分散されてなる、請求項1に記載の親水化処理剤。
- 前記水難溶性のセリウム化合物(A)が、炭酸セリウム(III)、フッ化セリウム(III)、フッ化セリウム(IV)及び酸化セリウム(IV)から選ばれる1種又は2種以上である、請求項1又は2に記載の親水化処理剤。
- さらに、前記水の中に、有機成分(B)から選ばれる1種又は2種以上を含有する、請求項1~3の何れか1項に記載の親水化処理剤。
- 金属材の表面に形成された親水性皮膜であって、水難溶性のセリウム化合物(A)から選ばれる1種又は2種以上を含有することを特徴とする親水性皮膜。
- 前記水難溶性のセリウム化合物(A)の含有量が、固形分比率で5~100質量%である、請求項5に記載の親水性皮膜。
- 前記水難溶性のセリウム化合物(A)が、炭酸セリウム(III)、フッ化セリウム(III)、フッ化セリウム(IV)及び酸化セリウム(IV)から選ばれる1種又は2種以上である、請求項5又は6に記載の親水性皮膜。
- さらに、有機成分(B)から選ばれる1種又は2種以上を含有する、請求項5~7の何れか1項に記載の親水性皮膜。
- 前記金属材の前記表面を、請求項1~4の何れか1項に記載の親水化処理剤で処理した後、乾燥して得られる、請求項5~8の何れか1項に記載の親水性皮膜。
- 金属材の表面の一部又は全部を、請求項1~4の何れか1項に記載の親水化処理剤で処理した後、乾燥して請求項5~9の何れか1項に記載の親水性皮膜を形成することを特徴とする親水化処理方法。
- 表面に請求項5~9の何れか1項に記載の親水性皮膜を設けた金属材。
- 前記金属材が、アルミニウム材、アルミニウム合金材、銅材、銅合金材の何れかである、請求項11に記載の金属材。
- 熱交換器の部材である、請求項11又は12に記載の金属材。
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EP2592131A3 (en) * | 2011-11-14 | 2013-06-12 | Advanced Technology Materials, Inc. | Aqueous cerium-containing solution having an extended bath lifetime for removing mask material |
WO2020129963A1 (ja) * | 2018-12-18 | 2020-06-25 | 東レ株式会社 | 酸化セリウムのナノ粒子、核酸の分解方法、ポリペプチドの分解方法、酸化セリウムのナノ粒子の製造方法、酸化剤、抗酸化剤、抗カビ剤および抗ウイルス剤 |
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61145263A (ja) * | 1984-12-19 | 1986-07-02 | Nippon Seihaku Kk | フイン材コ−テイング用組成物 |
JPH05222334A (ja) | 1992-02-07 | 1993-08-31 | Nippon Paint Co Ltd | 親水性表面処理剤、親水性表面処理浴、及び親水性表面処理方法 |
JPH05302042A (ja) | 1992-04-24 | 1993-11-16 | Nippon Paint Co Ltd | アルミニウム製熱交換器用親水化表面処理剤、及び親水化表面処理方法 |
JP2000171191A (ja) | 1998-12-07 | 2000-06-23 | Nippon Parkerizing Co Ltd | 抗菌防かび性に優れたアルミニウム合金製フィン材、及びそれを具備するエアコンディショナー用熱交換器 |
JP2000248381A (ja) * | 1999-02-26 | 2000-09-12 | Nippon Light Metal Co Ltd | アルミニウム材の親水性処理方法及びその下地処理剤並びに親水性塗料 |
JP2001089752A (ja) * | 1995-12-22 | 2001-04-03 | Toto Ltd | 光半導体の光励起に応じて親水化される部材及びその製造方法 |
JP2002105241A (ja) | 2000-07-12 | 2002-04-10 | Dainichiseika Color & Chem Mfg Co Ltd | 水性溶液組成物および物品の表面改質方法 |
JP2005054116A (ja) * | 2003-08-06 | 2005-03-03 | Univ Nihon | 硬質塗膜の製造方法 |
JP2006078134A (ja) | 2004-09-13 | 2006-03-23 | Matsushita Electric Ind Co Ltd | アルミニウムフィン材 |
JP2007313422A (ja) * | 2006-05-25 | 2007-12-06 | Matsushita Electric Works Ltd | 易水洗性被膜の製造方法及び物品 |
JP2009506186A (ja) * | 2005-08-30 | 2009-02-12 | ラペイル | 少なくとも一つのウレイド官能基を担持したラテックス組成物の、木材に接着させるための使用 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997023572A1 (fr) * | 1995-12-22 | 1997-07-03 | Toto Ltd. | Procede photocatalytique pour rendre une surface hydrophile et materiau composite ayant une surface rendue hydrophile par un processus photocatalytique |
JP3962123B2 (ja) * | 1997-06-09 | 2007-08-22 | 新日本製鐵株式会社 | 有機系表面処理金属板および有機系金属表面処理液 |
KR100775228B1 (ko) * | 1996-09-30 | 2007-11-12 | 히다치 가세고교 가부시끼가이샤 | 산화세륨 연마제 및 기판의 연마법 |
JP3746400B2 (ja) * | 1999-06-29 | 2006-02-15 | 三菱製紙株式会社 | インクジェット記録媒体 |
JP4532690B2 (ja) * | 2000-07-24 | 2010-08-25 | 新日本製鐵株式会社 | 樹脂系耐食性層を有する金属材 |
JP3772658B2 (ja) * | 2000-09-13 | 2006-05-10 | 東陶機器株式会社 | 光触媒性コーティング組成物 |
US6586483B2 (en) * | 2001-01-08 | 2003-07-01 | 3M Innovative Properties Company | Foam including surface-modified nanoparticles |
JP2002294175A (ja) * | 2001-03-28 | 2002-10-09 | Nippon Paint Co Ltd | 陰極電着塗料組成物 |
BE1015823A3 (fr) * | 2003-12-17 | 2005-09-06 | Ct Rech Metallurgiques Asbl | Procede de revetement d'une surface metallique par une couche ultrafine. |
JP2006176635A (ja) * | 2004-12-22 | 2006-07-06 | Matsushita Electric Works Ltd | 水系親水性塗料組成物およびこれを用いた塗装品 |
ES2562407T3 (es) * | 2005-01-07 | 2016-03-04 | Rhodia Chimie | Composiciones de pintura acuosas que comprenden una dispersión coloidal de cerio |
US8197613B2 (en) * | 2005-06-14 | 2012-06-12 | Material Interface, Inc. | Nanoparticle surface treatment |
KR100812052B1 (ko) * | 2005-11-14 | 2008-03-10 | 주식회사 엘지화학 | 탄산세륨 분말, 산화세륨 분말, 그 제조방법, 및 이를포함하는 cmp 슬러리 |
EP2001811A4 (en) * | 2006-03-30 | 2011-07-06 | Rhodia | MODIFIED SURFACES AND METHOD FOR MODIFYING A SURFACE |
EP2099953B1 (en) * | 2006-09-29 | 2019-04-03 | Momentive Performance Materials Inc. | Storage stable composition of partial and/or complete condensate of hydrolyzable organofunctional silane |
JP4719662B2 (ja) * | 2006-11-21 | 2011-07-06 | 日本パーカライジング株式会社 | 環境対応型プレコート金属材料用水系表面処理剤、並びに表面処理金属材料及び環境対応型プレコート金属材料 |
JP5089316B2 (ja) * | 2007-10-02 | 2012-12-05 | 日本ペイント株式会社 | 金属表面処理組成物、この組成物を用いたアルミニウム系金属基材の表面処理方法、及びこの方法を用いて製造されたアルミニウム系金属表面処理基材 |
WO2010007882A1 (ja) * | 2008-07-16 | 2010-01-21 | 日本パーカライジング株式会社 | 水系金属表面処理剤及び表面処理金属材料 |
-
2010
- 2010-10-19 JP JP2010234993A patent/JP2012087213A/ja active Pending
-
2011
- 2011-10-18 BR BR112013009683A patent/BR112013009683A2/pt not_active IP Right Cessation
- 2011-10-18 KR KR1020137012583A patent/KR101512914B1/ko not_active IP Right Cessation
- 2011-10-18 AU AU2011319006A patent/AU2011319006A1/en not_active Abandoned
- 2011-10-18 US US13/878,923 patent/US20130196167A1/en not_active Abandoned
- 2011-10-18 CN CN2011800493323A patent/CN103154167A/zh active Pending
- 2011-10-18 WO PCT/JP2011/073889 patent/WO2012053497A1/ja active Application Filing
- 2011-10-18 EP EP11834336.7A patent/EP2639274A4/en not_active Withdrawn
- 2011-10-19 TW TW100137892A patent/TW201229223A/zh unknown
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61145263A (ja) * | 1984-12-19 | 1986-07-02 | Nippon Seihaku Kk | フイン材コ−テイング用組成物 |
JPH05222334A (ja) | 1992-02-07 | 1993-08-31 | Nippon Paint Co Ltd | 親水性表面処理剤、親水性表面処理浴、及び親水性表面処理方法 |
JPH05302042A (ja) | 1992-04-24 | 1993-11-16 | Nippon Paint Co Ltd | アルミニウム製熱交換器用親水化表面処理剤、及び親水化表面処理方法 |
JP2001089752A (ja) * | 1995-12-22 | 2001-04-03 | Toto Ltd | 光半導体の光励起に応じて親水化される部材及びその製造方法 |
JP2000171191A (ja) | 1998-12-07 | 2000-06-23 | Nippon Parkerizing Co Ltd | 抗菌防かび性に優れたアルミニウム合金製フィン材、及びそれを具備するエアコンディショナー用熱交換器 |
JP2000248381A (ja) * | 1999-02-26 | 2000-09-12 | Nippon Light Metal Co Ltd | アルミニウム材の親水性処理方法及びその下地処理剤並びに親水性塗料 |
JP2002105241A (ja) | 2000-07-12 | 2002-04-10 | Dainichiseika Color & Chem Mfg Co Ltd | 水性溶液組成物および物品の表面改質方法 |
JP2005054116A (ja) * | 2003-08-06 | 2005-03-03 | Univ Nihon | 硬質塗膜の製造方法 |
JP2006078134A (ja) | 2004-09-13 | 2006-03-23 | Matsushita Electric Ind Co Ltd | アルミニウムフィン材 |
JP2009506186A (ja) * | 2005-08-30 | 2009-02-12 | ラペイル | 少なくとも一つのウレイド官能基を担持したラテックス組成物の、木材に接着させるための使用 |
JP2007313422A (ja) * | 2006-05-25 | 2007-12-06 | Matsushita Electric Works Ltd | 易水洗性被膜の製造方法及び物品 |
Non-Patent Citations (4)
Title |
---|
ANTIBACTERIAL AND ANTIFUNGAL AGENTS, vol. 21, no. 7, 1993, pages 385 - 389 |
ANTIBACTERIAL AND ANTIFUNGAL AGENTS, vol. 22, no. 5, 1994, pages 277 - 282 |
ANTIBACTERIAL AND ANTIFUNGAL AGENTS, vol. 36, no. 6, 2008, pages 359 - 363 |
See also references of EP2639274A4 * |
Cited By (7)
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EP2592131A3 (en) * | 2011-11-14 | 2013-06-12 | Advanced Technology Materials, Inc. | Aqueous cerium-containing solution having an extended bath lifetime for removing mask material |
US8618036B2 (en) | 2011-11-14 | 2013-12-31 | International Business Machines Corporation | Aqueous cerium-containing solution having an extended bath lifetime for removing mask material |
WO2020129963A1 (ja) * | 2018-12-18 | 2020-06-25 | 東レ株式会社 | 酸化セリウムのナノ粒子、核酸の分解方法、ポリペプチドの分解方法、酸化セリウムのナノ粒子の製造方法、酸化剤、抗酸化剤、抗カビ剤および抗ウイルス剤 |
JPWO2020129963A1 (ja) * | 2018-12-18 | 2021-10-21 | 東レ株式会社 | 酸化セリウムのナノ粒子、核酸の分解方法、ポリペプチドの分解方法、酸化セリウムのナノ粒子の製造方法、酸化剤、抗酸化剤、抗カビ剤および抗ウイルス剤 |
US11937598B2 (en) | 2018-12-18 | 2024-03-26 | Toray Industries, Inc. | Cerium oxide nanoparticle, decomposition method of nucleic acid, decomposition method of polypeptide, method of producing cerium oxide nanoparticle, oxidizing agent, antioxidant, antifungal agent, and anti-virus agent |
JP7508780B2 (ja) | 2018-12-18 | 2024-07-02 | 東レ株式会社 | 酸化セリウムのナノ粒子、酸化セリウムのナノ粒子の製造方法、ポリペプチドの分解方法、酸化酵素代替物、漂白剤、消毒剤、抗酸化酵素代替物、ラジカル消去剤、抗カビ剤および抗ウイルス剤 |
EP4121396A4 (en) * | 2020-03-20 | 2024-07-03 | Univ California | AQUEOUS DISPERSION OF CER(III) CARBONATE PARTICLES |
Also Published As
Publication number | Publication date |
---|---|
TW201229223A (en) | 2012-07-16 |
EP2639274A4 (en) | 2014-06-11 |
KR101512914B1 (ko) | 2015-04-16 |
BR112013009683A2 (pt) | 2016-07-12 |
JP2012087213A (ja) | 2012-05-10 |
EP2639274A1 (en) | 2013-09-18 |
CN103154167A (zh) | 2013-06-12 |
AU2011319006A1 (en) | 2013-05-02 |
KR20130084667A (ko) | 2013-07-25 |
US20130196167A1 (en) | 2013-08-01 |
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