WO1996021523A1 - Procede permettant de rendre hydrofuge une surface metallique et materiau metallique extremement hydrofuge - Google Patents

Procede permettant de rendre hydrofuge une surface metallique et materiau metallique extremement hydrofuge Download PDF

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Publication number
WO1996021523A1
WO1996021523A1 PCT/JP1996/000024 JP9600024W WO9621523A1 WO 1996021523 A1 WO1996021523 A1 WO 1996021523A1 JP 9600024 W JP9600024 W JP 9600024W WO 9621523 A1 WO9621523 A1 WO 9621523A1
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Prior art keywords
metal
water
uneven structure
repellent
metal material
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PCT/JP1996/000024
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English (en)
Japanese (ja)
Inventor
Satoshi Shibuichi
Tomohiro Onda
Kaoru Tsujii
Takamasa Yamamoto
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Kao Corporation
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Publication of WO1996021523A1 publication Critical patent/WO1996021523A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • 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

Definitions

  • the present invention relates to a method for imparting liquid repellency to a metal surface, and in particular, to products requiring liquid repellency, for example, kitchen products such as tables, trays, sinks, bulletin boards such as road signs, and electronic products for mobile phones.
  • the present invention relates to a method for imparting liquid repellency which can be applied to the surface treatment of metal surfaces such as fins for heat exchangers and flowing liquid tubes.
  • the present invention also relates to the application of the metal material imparted with water repellency as described above to a snow-resistant / ice-resistant material and an anti-snow material against ice and snow. Background art
  • an object of the present invention is to provide a method capable of imparting high liquid repellency to a metal surface at low cost and simply. Disclosure of the invention
  • liquid repellency was improved by forming a multi-period structure including a long-period uneven structure and a small-period uneven structure in the structure.
  • the metal having the super water-repellent surface when placed on an ice-snow surface, it has extremely high frictional properties, very little icing or snow accretion on the surface, and when the temperature rises to zero degrees Celsius or higher, ice and snow may be generated.
  • the present inventors have found that water does not cover the surface even when it is melted, does not damage the road surface or floor surface, and is an ideal anti-snow and anti-slip metal material, thus completing the present invention.
  • the present invention is characterized in that a liquid-repellent substance is coated on all or a part of a metal surface having a fine uneven structure on the surface and having a contact angle with water of 30 ° or less.
  • the present invention provides a method for imparting liquid repellency to a metal surface.
  • the present invention is characterized in that a metal surface having a fine uneven structure on the surface and a contact angle with water of 30 ° or less has a super water-repellent surface coated with a water-repellent substance.
  • the present invention provides a super-water-repellent metal material.
  • the present invention is characterized by having a super-water-repellent surface formed by coating a water-repellent substance on a metal surface having a fine concavo-convex structure and having a contact angle to water of 30 degrees or less. It provides a snow-resistant and ice-resistant metal material.
  • the present invention is characterized in that it has a super-water-repellent surface formed by coating a water-repellent substance on a metal surface having a fine uneven structure and a contact angle to water of 30 degrees or less.
  • the present invention provides an anti-skid metal material for ice and snow.
  • the present invention provides a method for imparting liquid repellency to a metal surface, which comprises coating a fluoroalkyl phosphate compound on all or a part of the metal surface. Is what you do.
  • the present invention provides a super lyophobic metal material having a super lyophobic surface coated with a fluoroalkyl phosphate compound on the metal surface.
  • FIG. 1 are diagrams showing a configuration of a main part of the contact angle measuring device and a contact angle.
  • FIG. 2 is a scanning electron micrograph of the acid-treated zinc plate surface in the example of the present invention.
  • FIG. 3 is a scanning electron micrograph of a surface of an aluminum plate that has been subjected to a heat treatment in an example of the present invention.
  • FIG. 4 is a scanning electron micrograph of the surface of a zinc plate in a cathode subjected to electrolysis treatment in an example of the present invention.
  • FIG. 5 is a scanning electron micrograph of the surface of an aluminum plate at the anode subjected to electrolysis treatment in the example of the present invention.
  • FIG. 6 is a diagram showing the shape of snow or ice used in the snow resistance test and the ice resistance test.
  • FIG. 7 is an explanatory diagram showing a method for testing snow resistance and ice resistance.
  • FIG. 8 is a diagram showing the shape of a metal plate used for measuring slipperiness on ice and snow.
  • FIG. 9 is a diagram showing the ice and snow surface preparation container used for the slip property measurement.
  • FIG. 10 is a scanning electron micrograph of the surface of a zinc plate in a cathode subjected to electrolysis treatment in Example 8.
  • FIG. 11 shows the results of dysman plotting of the contact angles of the zinc plate obtained in Example 8 with various liquids.
  • FIG. 12 is a scanning electron micrograph of the surface of the aluminum plate at the anode subjected to the electrolysis treatment in Example 9.
  • FIG. 13 shows the results of dismantling the contact angles of the aluminum plate obtained in Example 9 with various liquids.
  • lyophobic refers to a case where the contact angle of a metal surface with a liquid is larger than 90 degrees, and such a surface is called a lyophobic surface.
  • the object of the present invention is not necessarily limited to a surface to which water adheres, but is also applied to increase a contact angle with a liquid containing alcohol, oil, and surfactant.
  • the liquid-repellent substance used in the final coating treatment of the metal surface is a substance having a contact angle of more than 90 degrees with respect to the liquid.
  • the contact angle to water is 30 degrees or less.
  • the actual surface area per cm 2 of the uneven structure in plan view is sufficiently large. Is generally preferred.
  • the liquid repellency is not improved.
  • the liquid repellency is affected by the density of the actual surface near the very surface of the uneven structure that can come in contact with the droplets, that is, the actual surface area per unit volume. It is preferred.
  • the height of the fine uneven structure on the surface is preferably 800 m or less, more preferably 300 m or less, and particularly preferably 30 um or less.
  • the actual surface area per cm 2 of the concavo-convex structure in plan view is large, specifically, 3 cm 2 or more.
  • the actual surface area of the uneven structure is preferably less than 2 Ocm 2 .
  • the contact ratio of the irregular surface i.e. the contact area of the concavo-convex structure when addressed a smooth rigid on its uneven surface, rigid surface 1 cm 2 per 0.2 cm 2 or less.
  • the actual surface area refers to the surface area measured by the BET method.
  • This BET method uses the BET adsorption formula proposed by S. B runauer, PH Emmett and E. Telel, based on the adsorption of gas molecules (nitrogen gas, krypton gas) on a solid surface. How to calculate the surface area of a solid It is. The height, width and contact area of the uneven structure were measured by image analysis from a cross-sectional SEM photograph of the solid.
  • the range of the width and height of the fine uneven structure formed on the metal surface is 1 to 800 m, more preferably 1 nm to 300 m, especially 50 to 30 m.
  • the structure need not be uniform.
  • the shape of the concavo-convex structure is not particularly limited, and may be any of scaly, prismatic, cylindrical, pyramidal, conical, and needle-like.
  • a fractal structure or a self-fine structure having a fractal dimension of two or more and less than three dimensions, which is formed by complicatedly combining those shapes, may be used.
  • the method for producing such a hydrophilic metal surface and it may be an artificially processed one or a naturally existing one.
  • methods of artificially processing include (1) a method of polishing or cutting the metal surface, (2) a method of immersing the metal surface in an acid or alkaline solution, and (3) a method of polishing the metal. (4) a method using metal as an electrode and utilizing electrolysis, and (5) a method based on metal structure.
  • Specific examples of the above (1) include a method of sanding with sandpaper or metal file, a method of sand blasting, or a method of cutting a V-groove or a cross hatch on a metal surface with a cutter.
  • the method (2) can be implemented, for example, by the following steps. Mix an acid such as hydrochloric acid and water, adjust the concentration to an appropriate pH between pH 1 and 6, immerse the target metal plate in this solution, and hold it at a specified temperature for a specified time As a result, a fine uneven structure is formed on the metal surface.
  • an alkali sodium hydroxide or the like is mixed with water, the concentration is adjusted to an appropriate pH between pH 8 and 14, and the target metal plate is immersed in this solution. By holding at a predetermined temperature for a predetermined time, a fine uneven structure is formed on the metal surface.
  • the method (4) there is a method in which a target metal plate is immersed in an electrolyte solution as an anode or a cathode, and a predetermined voltage is applied between both electrodes at a predetermined temperature for a predetermined time. At this time, a method of forming a concavo-convex structure by eluting metal from the target metal plate And a method of forming a concavo-convex structure by depositing a metal or other substance in an electrolyte solution on a target metal plate. Examples of the former include electrolytic polishing, and the latter include electroplating and electrodeposition coating.
  • the above method (5) can be carried out, for example, by the following steps: a liquid having a target metal heated to above its melting point and melted in a mold having fine irregularities on the c surface. By pouring it into metal, and then cooling and solidifying it, it is possible to obtain a metal surface with the ⁇ -shaped fine uneven structure transferred to the surface.
  • the metal used in the present invention is not particularly limited as long as a fine uneven structure is formed by the above-mentioned processes (1) to (5).
  • the metal used in the above-mentioned processes (2) to (4) is not particularly limited. Suitable metals include zinc, nickel, iron, aluminum or their alloys, stainless steel and the like.
  • a liquid-repellent surface can be obtained by coating such a hydrophilic metal surface with a liquid-repellent substance.
  • the thickness of the coating layer at this time is not particularly limited as long as it does not eliminate fine irregularities on the surface, and is preferably 100 nm or less.
  • a heat-proof treatment such as chromate treatment can be performed prior to or simultaneously with the treatment with these liquid repellent substances.
  • the liquid-repellent substance used in the present invention may be any substance that has a hydrophobic group or the like by reacting with a functional group (for example, a hydroxyl group) on a metal surface, and is not limited.
  • a functional group for example, a hydroxyl group
  • the c- silane coupling agent include a coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, an isocyanate-based coupling agent, and a zirconium-based coupling agent.
  • Examples include trichloroalkylsilanes of the formula (1), trimethoxyalkylsilanes of the formula (2), and triethoxyquinalkylsilanes of the formula (3).
  • n is an integer of 6 to 20.
  • a reaction part reacting with a functional group on the metal surface (C 1 group, ⁇ CH 3 group, respectively) , OC 2 H 5 groups) and one water-phobic part (long-chain alkyl group) for imparting water repellency.
  • a functional group on the metal surface C 1 group, ⁇ CH 3 group, respectively
  • OC 2 H 5 groups a water-phobic part
  • the structure of the hydrophobic part may be different.
  • some or all of the hydrogen atoms in the hydrophobic portion may be replaced by fluorine atoms, as in the alkyltrichlorosilane fluoride represented by the following formula (4).
  • titanate-based coupling agents are not limited to the following examples, and typical ones are isopropylpropylisostearoyl titanate, isopropyltrioctynol titanate, and isopropyl alcohol represented by the following formula (5).
  • Aluminum-based coupling agent examples include an acetoalkoxyaluminum diisopropylate represented by the following formula (6).
  • the treatment using the silane coupling agent is performed, for example, as follows.
  • a mixture of hexadecane and a mixture of formaldehyde and carbon tetrachloride is dried over molecular solvent, and an appropriate amount of a silane coupling agent is added to the dried solvent to obtain a treatment solution.
  • the treatment is carried out by immersing a metal having a concavo-convex structure in a dry atmosphere at an appropriate temperature for a predetermined time. After immersion, wash with black mouth form and water and dry.
  • the treatment using a titanate-based coupling agent or an aluminum-based force-binding agent is performed, for example, as follows. Toluene is dried with a molecular sieve or the like, and an appropriate amount of a titanate-based coupling agent or an aluminum-based coupling agent is added to the dried toluene to obtain a treatment solution.
  • the treatment is carried out by immersing a metal having an uneven structure at a suitable temperature for a predetermined time in a dry atmosphere. After immersion, wash with an appropriate organic solvent or an aqueous solution containing an activator for washing, wash with water and dry under appropriate conditions.
  • a fluoroalkyl phosphate compound is used as a coating agent.
  • excellent liquid repellency can be obtained even when the metal surface is smooth or has a fine uneven structure as described above.
  • the contact angle is larger than 90 degrees, the contact angle is further increased, and when the contact angle of the droplet on the flat solid surface is less than 90 degrees, the contact angle is further decreased.
  • a mono (fluoroalkyl) phosphate, a di (fluoroalkyl) phosphate or a salt thereof is preferable, and a mono (C 6 -C 36 fluoroalkyl) is particularly preferable.
  • Phosphate esters, di (C 6 -C 36 fluoroalkyl) phosphate esters or salts thereof are preferred. More specifically, a monofluoroalkyl phosphate represented by the following general formula (7)
  • R f represents a linear or branched fluoroalkyl group
  • X represents any one of a hydrogen atom, an alkali metal, an alkaline earth metal, ammonia, and an alkylammonium having 1 to 4 carbon atoms.
  • the linear or branched fluoroalkyl group represented by R f has 6 to 36 carbon atoms from the viewpoint of ease of synthesis, and further has 8 to 36 carbon atoms from the viewpoint of liquid repellency.
  • R may be a perfluoroalkyl group composed of only carbon atoms and fluorine atoms, or a fluoroalkyl group in which a part of hydrogen is replaced by fluorine.
  • the proportion of fluorine is large, and it is particularly preferable that the terminal group is a CF 3 — group.
  • Examples of the alkali metal represented by X include sodium, potassium, rubidium, cesium, and the like.
  • Examples of the alkaline earth metal include calcium, potassium, stomium, and the like.
  • Examples of the alkylammonium (4) include monomethylamine, dimethylamine, trimethylamine, monoethylamine, dimethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine and the like and proton. Alkyl ammonium formed. From the viewpoints of stability and easiness of treatment, X is most preferably a hydrogen atom.
  • a coating method using a c -fluoroalkyl phosphate compound for example, (1) a fluoroalkyl phosphate compound (2) a method of applying the treatment liquid directly to the metal surface, (3) a method of immersing a piece of metal in the treatment liquid and applying a voltage between them.
  • a method of applying the voltage to perform electrolysis is exemplified.
  • the solvent used in this treatment liquid is not particularly limited as long as it is a solvent that can dissolve the fluoroalkyl phosphatase, and examples thereof include alcohol, ether, and fluorocarbon.
  • the fluoroalkyl phosphoric acid ester is usually incorporated in an amount of 0.01 to 50% by weight, preferably 0.1 to 10% by weight.
  • the method (1) can be carried out, for example, by adsorbing the fluoroalkyl phosphate on the metal surface by holding the metal plate in the above-mentioned treatment solution at a predetermined temperature for a predetermined time. .
  • the above treatment liquid is directly applied to a metal surface with a brush, a brush, or the like, or is sprayed or sprayed on a metal surface, and then the metal is exposed to air.
  • the method (3) which can be carried out by allowing the solvent to evaporate after standing for a predetermined period of time, can be performed, for example, by treating the above-mentioned processing solution with the metal to be provided with liquid repellency as the positive electrode and the other metal as the negative electrode. Immersed, prescribed voltage between both electrodes at prescribed temperature at prescribed temperature
  • the application can be carried out by adsorbing fluoroalkyl phosphate ester on the metal surface on the anode side by applying for a time.
  • the metal material obtained as described above has excellent liquid repellency (especially water repellency), and is useful as a material requiring various liquid repellencies.
  • the metal material of the present invention has sufficient mechanical strength, is inexpensive, and has excellent resistance to snow and ice, and is suitable for shelves, luggage, antennas, and capes in a freezing warehouse. It can be widely used as a material for saws, steel towers, jigs for civil engineering machinery, houses and roofs.
  • the frictional force is significantly reduced on frozen ground in cold regions, snowy surfaces in snowy countries, and frozen floors in refrigeration warehouses. It is dangerous because people fall down when walking. In order to prevent such dangers, it has been a conventional method to create an uneven structure on a solid surface in order to increase the frictional force between the contacting surfaces. In extreme cases, spikes and needle-like projections are formed on the soles of the shoes to prevent slippage on ice and snow.
  • the anti-skid anti-slip metal material of the present invention despite having no sharp projections, produces high friction on the ice and snow surface, so that shelves, luggage, shoes, and vehicles in a freezing warehouse can be used. It can be used as an anti-slip material for surfaces that come in contact with metal such as ice or snow such as a ring. Further, icing and snow accretion on the surface of the metal material of the present invention are extremely small, and even if the temperature becomes zero degrees Celsius or higher and the ice and snow melts, water does not cover the surface, and the road surface and floor surface are damaged. Absent.
  • liquid-repellent metal surface obtained according to the present invention is used for the air-side heat transfer surface of a heat exchanger such as an air conditioner or a refrigerator, a frost formation phenomenon can be suppressed for a long time. As a result, the reduction in heat exchange efficiency due to frost formation can be reduced.
  • liquid-repellent metal surface obtained by the present invention is used as a contact surface with a liquid of a pipe (flowing pipe) through which liquid flows, such as a water pipe or a funnel, the flow of the liquid is reduced.
  • a pipe flowing pipe
  • a flow tube that is fast and free of liquid after use can be obtained.
  • Coupling is performed by mixing 300 g of hexadecane (manufactured by Tokyo Chemical Industry), 30 g of carbon tetrachloride (manufactured by Kanto Chemical Co., Ltd.), and 30 g of Kuroguchi Holm (manufactured by Kanto Chemical Co., Ltd.). Add about 1 g of 1H, 1H, 2H, 2H-perfluorooctyltrichlorosilane to the solvent dehydrated with molecular sieve 3A, and immerse the zinc plate in a dry nitrogen atmosphere at room temperature for 12 hours. By I went. After the coupling treatment, the membrane was washed twice with a black-mouthed form 300, air-dried, further washed with water, and air-dried.
  • the contact angle of the metal surface to distilled water was measured using an optical contact angle meter (CA-A, manufactured by Kyowa Interface Science Co., Ltd.). That is, as shown in FIGS. 1 (a) and 1 (b), test sample 1 was placed on sample stage 2 of the above-mentioned optical contact angle meter, and distilled water was poured into syringe 3 for dropping droplets. A droplet 4 having a diameter of l mm was formed at the tip of the needle of the nozzle 3. The gap between the liquid drop 4 and the test sample 1 was maintained at about 1 cm, and the syringe 3 was vibrated to drop the drop 4 at the needle tip onto the test sample 1. After dropping the droplet 4, the contact angle (0) between the droplet 4 and the test sample 1 was measured.
  • CA-A optical contact angle meter
  • the contact angle of water on a flat zinc plate was 79 degrees, but by polishing the zinc plate with a paper file, the contact angle to water was reduced to 29 degrees, resulting in a hydrophilic surface.
  • a water-repellent surface having a contact angle to water of 141 degrees was obtained.
  • the contact angle with water was only 105 degrees, and sufficient water repellency was not obtained.
  • the height of the irregularities on the surface of the zinc plate is 1 ⁇ m or less, the width is 300 ⁇ m or more, the actual surface area per 1 cm 2 in plan view is 1.0 to 1.2 cm 2 , and the contact area was 0.6 cm 2 or more.
  • a zinc plate (manufactured by Niraco) having a size of 30 cm x i 0 cm and a thickness of 0.3 was immersed in an aqueous solution adjusted to pH 3 with hydrochloric acid at room temperature for 3 days.
  • a fine concave-convex structure was formed as shown in FIG. Height 2-5 0 ⁇ m of this concavo-convex structure, the width 0. 5 to 2 5 // m, the actual surface area per 1 cm 2 in plan view 1 6. 2 cm 2, the contact area is 0. It was 0.43 cm 2 .
  • the surface was made liquid-repellent by a cutting treatment using octyl decyltrichlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.).
  • the coupling treatment was performed by mixing 300 g of hexadecane (Tokyo Kasei Co., Ltd.), 30 g of carbon tetrachloride (Kanto Chemical Co., Ltd., special grade), and 30 g of Kuroguchi Holm (Kanto Chemical Co., Ltd., special grade).
  • dehydrating the solvent with molecular sieve 3 A Approximately 1 g of decyltrichlorosilane was added, and the zinc plate was immersed in the treatment solution for 12 hours in a dry nitrogen atmosphere at room temperature. After the treatment, the membrane was washed twice with a black form 300 and air-dried at room temperature. After drying, the sample was washed with water and air dried again at room temperature.
  • the contact angle of the zinc plate sample thus obtained with water and glycerin was measured using an optical contact angle measuring device (CA-A type, manufactured by Kyowa Interface Science Co., Ltd.).
  • the contact angle of water on a flat zinc plate was 79 degrees, but by immersing it in acid, the contact angle with water was reduced to 16 degrees, resulting in a hydrophilic surface.
  • silane coupling treatment a liquid-repellent surface having a contact angle of 160 degrees with water and a contact angle of 155 degrees with glycerin was obtained.
  • the surface was made water-repellent by a coupling treatment using isopropyltriisostearoyl titanate (variety: KR-TTS, manufactured by Ajinomoto Co.). Coupling is performed using toluene (special grade, manufactured by Wako) dehydrated using molecular sieve 3A (manufactured by Wako). 5 g were mixed, and an aluminum plate was immersed in the treatment liquid at a temperature of 100 ° C. for 5 hours. After the coupling treatment, the membrane was washed twice with toluene ⁇ , dried at room temperature, further washed with water, and air-dried at room temperature.
  • KR-TTS isopropyltriisostearoyl titanate
  • the contact angle of the aluminum sample thus obtained with water was measured using an optical contact angle measuring device (CA-A type, manufactured by Kyowa Interface Science Co., Ltd.).
  • the contact angle of water on a flat aluminum plate was 70 degrees, but by immersing it in an alkaline solution, the contact angle with water was reduced to less than 3 degrees, and the hydrophilicity was reduced.
  • Surface By treating the hydrophilic surface with a titanate-based coupling agent, A water-repellent surface having a contact angle of 158 degrees was obtained.
  • An iron plate (manufactured by Niraco Co., Ltd.) with a size of 30 cm, 10 cm and a thickness of 0.3 cm is immersed in a 3% by weight saline solution, taken out, and left in the air for 2 weeks to corrode the surface.
  • fine uneven structure (height 2 to 20 ⁇ 1, width 0.5 to 30 / m, actual surface area per 1 cm 2 in plan view 13.7 cm 2 , contact area 0.0 0.5 cm 2 ) was formed and subjected to a coupling treatment using octadecyl trichlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) to make the surface water-repellent.
  • the coupling treatment is performed by mixing 300 g of hexadecane (manufactured by Tokyo Chemical Industry), 30 g of carbon tetrachloride (manufactured by Kanto Chemical Co., special grade), and 30 g of Kuroguchi Form (manufactured by Kanto Chemical Co., Ltd.). Approximately 1 g of octyl decyl trichlorosilane was added to the solvent dehydrated with molecular sieve 3A, and the steel plate was immersed in a dry nitrogen atmosphere at room temperature for 12 hours. After the coupling treatment, the membrane was washed twice with a black-mouthed form 300 and air-dried.
  • the contact angle of the iron plate sample thus obtained with water was measured using an optical contact angle measuring device (CA-A type, manufactured by Kyowa Interface Science Co., Ltd.). Although the contact angle of water on a flat iron plate was 83 degrees, the natural corrosion of the water reduced the contact angle to water to less than 3 degrees, resulting in a hydrophilic surface. By treating the hydrophilic surface with a silane-based coupling agent, a water-repellent surface having a contact angle to water of 160 degrees was obtained.
  • the liquid repellency was achieved by a coupling treatment using octadecyl trichlorolanne (manufactured by Tokyo Chemical Industry Co., Ltd.).
  • the coupling treatment is performed by mixing 300 g of hexadecane (manufactured by Tokyo Kasei Co., Ltd.), 30 g of carbon tetrachloride (manufactured by Kanto Chemical Co., Ltd., special grade), and 30 g of Kuroguchi Form (manufactured by Kanto Chemical Co., Ltd., special grade).
  • the contact angle of the zinc plate sample thus obtained with water and glycerin (Kanto Chemical Co., Ltd., special grade) wetting index standard solutions No. 54 and No. 48 (Wako Co., Ltd.) was determined by the optical contact angle.
  • the measurement was performed using a measuring device (manufactured by Kyowa Interface Science Co., Ltd., CA-A type).
  • the contact angle of water on a flat zinc plate was 79 degrees, but by electrolyzing it, the contact angle with water was reduced to less than 3 degrees, resulting in a hydrophilic surface.
  • a silane coupling agent By treating the hydrophilic surface with a silane coupling agent, a lyophobic surface having contact angles with various liquids shown in Table 1 was obtained.
  • Table 1 Water Glycerin Wetting Index Standard Solution Wetting Index Standard Solution
  • Example 5 two pieces of Lumidium (manufactured by Niraco Co., Ltd.) of size 3 Ocm x 10 cm and thickness 1 were used instead of the zinc plate, and 25 N-sulfuric acid 5 was used instead of the aqueous zinc chloride solution. Except for using a mixture of 1 liter of ion-exchanged water, installation was performed in the same manner as in Example 5, and an electrode current density of 1 OmAZcm was obtained using a stabilized DC power supply (manufactured by Instek, Inc., GPS-3300). 2 for 3 hours. As a result, aluminum was eluted from the aluminum plate surface of the anode, and a fine uneven structure was formed on the surface.
  • a stabilized DC power supply manufactured by Instek, Inc., GPS-3300
  • the liquid repellency was achieved by a force ring treatment using 1 H, 1 H, 2 H, 2 H-perfluorooctyl trichlorosilane (manufactured by PCR).
  • Coupling treatment is as follows: Hexadecane (Tokyo Kasei) 300 g, carbon tetrachloride (Kanto Chemical Co., special grade) 30 g, Kuroguchi Holm (Kanto Chemical Co., special grade) 30 g About 1 g of 1 H, 1 H, 2 H, 2 H-perfluorooctyl trichlorolane was added to the solvent mixed and dehydrated with 1 A sieve 3 A, and the aluminum plate used as the anode was dried at room temperature.
  • the contact angle of water on a flat aluminum plate was 70 degrees, but by electrolyzing it, the contact angle with water was reduced to less than 3 degrees, resulting in a hydrophilic surface. .
  • a silane coupling agent By treating the hydrophilic surface with a silane coupling agent, a lyophobic surface having contact angles with various liquids shown in Table 2 was obtained. Table 2
  • the ice used for the evaluation of ice resistance was a block-shaped ice with a side of 2 cm (ice machine; manufactured by HOSH I ZAK I, manufactured by IM-200 DWJ). As shown in Fig. 6, a slice of ice, crushed to a maximum length of 1 cm, was used.
  • a slice of ice, crushed to a maximum length of 1 cm was used.
  • natural snow Fukushima Prefecture, Taikura Ski Resort
  • the super-hydrophobic zinc plate obtained as described above is placed horizontally on the ground as shown in Fig.7. Then, snow or ice 1 is placed on sample plate 2 and sample plate 2 is gradually tilted. Then, the angles 0 SI and P at which the snow or ice 1 started to slide were recorded.
  • the water-repellent zinc plate obtained as in Example 2 is horizontally placed on the ground as shown in FIG. After that, snow or ice 1 is placed on the sample plate 2, and the sample plate 2 is gradually tilted. Then, the angle at which snow or ice 1 starts to slide 0 S 11 . was recorded. Under the temperature of 5 C, the block ice started to slide at 24 degrees in S S ,, P. 0 SI , P slipped at 24 degrees on the salmon ice, and S sll P against snow (temperature of 2 ° C) was 20 degrees. I went there, block ice And 0 sli P for snow ice is 50 degrees or more, and 0 sli P for snow is 90 degrees.
  • the water-repellent aluminum plate obtained as in Example 3 is horizontally placed on the ground as shown in FIG. After that, snow or ice 1 is placed on the sample plate 2, and the sample plate 2 is gradually tilted. Then, the angles 0 SI and P at which the snow or ice 1 started to slide were recorded. Under the condition of a temperature of 1-5 ° C, the block ice started to slide at 24 degrees in S S 1 and P. 0 sli P slipped at 24 degrees on the Zarame ice, and 0 sli P for snow (temperature 2 ° C) was 20 to 22 degrees. As a comparative example, a similar experiment was performed on an untreated flat aluminum plate. As a result, 0 sli P for block ice and flounder ice was 50 degrees or more, and 0 sli P for snow was 90 degrees.
  • the water-repellent iron plate obtained as in Example 4 is horizontally placed on the ground as shown in FIG. Then, snow or ice 1 is placed on sample plate 2 and sample plate 2 is gradually tilted. Then, the angle at which snow or ice 1 starts to slide is 0 sll . Was recorded. At a temperature of 15 ° C, the block ice began to slide at 0 sli P at 16-17 ° C. 0 sl , P slipped at 16 to 17 degrees on the salam ice, and 0 SI , P for snow (temperature 2 ° C) was 16 to 20 degrees. As a comparative example, a similar experiment was performed on an untreated flat iron plate, and the value of 0 sli P for block ice and flounder ice was 60 degrees or more, and that for snow was 90 degrees.
  • the water-repellent zinc plate obtained as in Example 5 is placed horizontally on the ground as shown in FIG. After that, snow or ice 1 is set on the sample plate 2, and the sample plate 2 is gradually tilted. Then, the angles S SI , P at which the snow or ice 1 started to slide were recorded. At a temperature of 5 ° C, the block ice began to slide at 25 s with 0 sli P.
  • the water-repellent aluminum plate obtained as in Example 6 is horizontally placed on the ground as shown in FIG. After that, snow or ice 1 is placed on the sample plate 2, and the sample plate 2 is gradually tilted. Then, angles 0 S 1 and P at which the snow or ice 1 starts to slide are recorded. Under the condition of a temperature of 1-5 ° C, the block ice started sliding at 0 sli P at 23 degrees. At Zara main ice Suberidashi at 0 sli P 2 three times, 0 sll P against the snow (air temperature 2 ° C) was 1. 6 degrees.
  • the microstructure before the silane coupling treatment was applied, and a similar experiment was performed on the hydrophilic surface.At a temperature of 15 ° C, S sli P for block ice was 50 ° C. On the other hand, 0 sli P for the salmon ice was 90 degrees, which means that the snow- and ice-resistance requires a fine structure on the surface and a chemical water-repellent treatment on the surface.
  • the water-repellent aluminum plate created in Example 6 was installed at an angle of 60 degrees with respect to the ground (Kao Corporation, at the site of Sakata Plant, at a temperature of 1), and the snow accumulation on the surface was checked. investigated. As a result, it was found that snow slipped off the surface of the water-repellent aluminum very quickly, and did not go off. As a comparative example, a similar experiment was performed on an aluminum plate obtained by performing coupling 'treatment on flat aluminum, and it was found that snow adhered to one surface.
  • the super-water-repellent zinc plate obtained as in Example 1 was bent at a length of 25 cm as shown in FIG. 8, and further placed in a container shown in FIG. 9 with block ice (2 cm square) and coarse ice (length lcm) or put snow and put a super water-repellent zinc plate on it. Then, gradually tilt the container containing block ice (2 cm square), coarse ice (about lcm in length), or snow, and the angle at which the super water-repellent zinc plate starts to slide 0 S 1 , P On the ice (5 ° C), 0 sli P started to slide at 20 to 30 degrees. On coarse ice (temperature 5 ° C), 0 sll P slipped at 33 degrees, and on snow (temperature 2 degrees), it slipped even at the measurement limit of 80 degrees.
  • the super-water-repellent zinc plate obtained as in Example 2 was processed as shown in FIG. 8, and further placed in a container shown in FIG. 9 in the form of block ice (2 cm square), coarse ice (about 1 cm in length), or Put snow in it and place a super water-repellent zinc plate on it. Then, gradually tilt the container containing block ice (2 cm square), coarse ice (about l cm in length), or snow, and the angle at which the super-water-repellent zinc plate starts to slide 0 sl , ⁇ As a result, on ice (temperature 5 ° C), ⁇ sli P started to slide at 20 to 30 degrees. On coarse ice (temperature 5 ° C), 0 sli P started to slip at about 30 ° C, and on snow (temperature 2 ° C), it did not slip even at the measurement limit of 80 ° C.
  • the super-water-repellent aluminum plate obtained as in Example 3 was processed as shown in FIG. 8, and further placed in a container shown in FIG. 9 in block ice (2 ( ⁇ square), coarse ice (length 1 cm). ) Or snow, put a super water-repellent aluminum plate on top of it, and gradually remove the container with block ice (2 cm square), coarse ice (about lcm in length), or snow. tilt go, angle S when the super water-repellent aluminum plate begins to slip
  • the super-water-repellent iron plate obtained as in Example 4 was processed as shown in FIG. 8, and further, block ice (2 cm square), coarse ice (about lcm in length), or snow was placed in the container shown in FIG. Put the super water-repellent iron plate on this. Then, gradually tilt the container containing block ice (2 cm square), coarse ice (about lcro in length), or snow, and measure the angle 0 S 1 , P when the super water-repellent iron plate starts to slide. However, on ice (temperature 5 ° C), s , i P began to slip when the temperature exceeded about 30 degrees. Even on coarse ice (temperature 5 ° C), S SI and P started to slide at 30 ° C, and on snow (temperature 2 ° C), they did not slip even at the measurement limit of 80 ° C.
  • the super-water-repellent zinc plate obtained as in Example 5 was processed as shown in FIG. 8 and further placed in a container shown in FIG. 9 in block ice (2 cm square), coarse ice (about lcm in length), or Put snow in it and place a super water-repellent zinc plate on it. Then, gradually tilt the container containing block ice (2 cm square), coarse ice (about 1 cm long), or snow, and set the angle 0 S when the super water-repellent zinc plate starts to slide. As a result of measurement, on ice (temperature 5 ° C), it started to slip at e sl , P or 30 degrees. Even on coarse ice (temperature 5 ° C), 0 sli P starts to slide at 30 degrees, and on snow (temperature At 2 ° C), it did not slip even at the measurement limit of 80 degrees.
  • S sli P was 7 degrees on coarse ice and 0 sli P was 10 to 12 degrees on snow.
  • a similar test was performed on a hydrophilic zinc plate having a microstructure, and although the value of 0 sli P was large and had an anti-slip effect, ice and snow adhered to the surface. Les, there was a practical problem.
  • the super-water-repellent aluminum plate obtained as in Example 6 was processed as shown in FIG. 8, and further placed in a container shown in FIG. 9 with block ice (2 cm square) and coarse ice (about 1 cm long). ) Put snow or snow and put super water-repellent aluminum plate on it. Then, gradually tilt the container containing block ice (2 cm square), coarse ice (about 1 cm in length), or snow, and set the angle 0 S , 1 P when the super water-repellent aluminum plate starts to slide. was measured on ice (temperature one 5 ° C) in 0 S li P began slipping in 2 8 °. Coarse ice (temperature one 5 ° C) at 0 S,, P is Suberidashi 3 twice, snow (temperature 2 ° C) in an even slip et become 8 0 degrees is the measurement limit Kaka ivy.
  • the mixture was placed in a reaction flask, mixed, heated to 70 ° C., and mixed for 12 hours. After cooling the reaction mixture to 60 ° C., 17 g of water was added and hydrolysis was carried out at 70 for 8 hours. After cooling to 30 ° C, getyl ether 350; ⁇ , water 18 and ethanol 70 mil were added, and the mixture was shaken to extract phosphoric acid into the lower layer.
  • the liquid repellency treatment of the OH metal surface was performed as follows. Smooth aluminum plate, stainless steel plate 18 and zinc plate (manufactured by Nikola) with a size of 10 cm x 5 cm and a thickness of 1. Omm are immersed in a 2.0 wt% ethanol solution of compound 7a for 1 week at room temperature. After washing with ethanol, it was dried.
  • the contact angle of the metal surface with respect to the liquid was measured using an optical contact angle meter (CA-A, manufactured by Kyowa Interface Science Co., Ltd.). That is, as shown in FIGS. 1 (a) and 1 (b), test sample 1 was placed on sample stage 2 of the above-mentioned optical contact angle meter, and the liquid was poured into syringe 3 for dropping liquid by 0.5 m. Then, a droplet 4 was formed at the tip of the syringe 3. The syringe 3 was slowly moved downward, and the droplet 4 was brought into contact with the test sample 1, and vibration was applied to place the droplet 4 on the test sample 1. At this time, the contact angle (0) between the droplet 4 and the test sample 1 was measured.
  • the liquids shown in Table 1 were used, and commercial grade products were used as they were. Table 3 shows the measurement results of the contact angles of each liquid on an aluminum plate, a stainless steel plate 18, and a zinc plate treated with liquid repellency with compound 7a.
  • Table 3 shows the measurement results of various liquids on an untreated smooth aluminum plate, stainless steel plate 18, and zinc plate (manufactured by Nilaco).
  • 2 ⁇ -Table 3
  • Aluminum plate Stainless steel 1 Zinc plate Untreated compound 7a treatment Untreated compound 7a treatment Untreated compound 7a treatment
  • the aluminum plate having the fine concavo-convex structure was immersed in a 2.0% by weight ethanol solution of compound 7a at room temperature for 1 week, washed with ethanol, and dried.
  • the contact angles of the aluminum plate treated in this manner with various liquids shown in Table 4 were measured.
  • the results are shown in Figure 13 in the form of a dysman plot.
  • the data of the smooth aluminum plate subjected to lyophobic treatment with the compound 7a shown in Example 7 is also shown by a white symbol.
  • treating a smooth aluminum plate with Compound 7a on an aluminum plate with fine irregularities has a much higher lyophobic property than treating it with Compound 7a.
  • liquid repellency can be imparted to various metal surfaces by a simple operation.
  • the metal material of the present invention is excellent in snow resistance and ice resistance: shelves and luggage in freezing warehouses, antennas, cables, steel towers, jigs for civil engineering machinery, houses, roofs, road signs, etc. It can be widely used as a material for bulletin boards.
  • the anti-snow and anti-slip metal material of the present invention has high friction on the ice and snow surface, despite having no sharp projections, so that shelves, luggage, shoes, and vehicle wheels in a freezing warehouse can be used. It can be used as a non-slip material for surfaces that come into contact with metal such as ice or snow.
  • icing and snow accretion on the surface of the metal material of the present invention are extremely small, Water does not cover the surface even if ice and snow melts at zero or more, and does not damage the road or floor.
  • liquid-repellent metal material obtained by the present invention is used for the air-side heat transfer surface of a heat exchanger such as an air conditioner or a refrigerator, it is possible to reduce the decrease in heat exchange efficiency due to frost formation. Can be.
  • liquid-repellent metal material obtained by the present invention may be used for a liquid-contacting surface of a pipe (flowing liquid pipe) through which liquid flows, such as a water pipe, a funnel, and a pouring port for various liquids.
  • a pipe flowing liquid pipe
  • the liquid repellent metal material obtained by the present invention is used for various electric devices such as a portable or indoor video, television, radio, etc., or an external part of a precision device such as a camera or a clock, thereby obtaining a device.
  • the inside can be shielded from tap water, rainwater, seawater, snow, etc. to prevent electric shock, short circuit or rust.
  • this unit may be used for electrical outlets such as outlets, sockets, water heaters, coffee makers, etc.
  • liquid-repellent metal material obtained by the present invention around handrails, doorknobs, and elevator push buttons, fingerprint dirt can be prevented.
  • liquid-repellent metal material obtained by the present invention in a part of an accessory or a watch that directly touches the human skin, it prevents sweat from adhering, and further prevents rash and rash. be able to.

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  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
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Abstract

Procédé permettant de rendre hydrofuge une surface métallique et consistant à appliquer une substance hydrofuge sur une partie ou sur la totalité d'une surface métallique présentant une structure à irrégularités fines et un angle de contact avec l'eau ne dépassant pas 30°; matériau hydrofuge obtenu selon ce procédé; et utilisation de ce matériau comme matériau métallique résistant au givrage et à la neige ou comme matériau métallique antidérapant par rapport à la neige et à la glace. L'invention se rapporte également à un procédé permettant de rendre hydrofuge une surface métallique, et consistant à appliquer, sur la surface, un revêtement de phosphate de fluoroalkyle.
PCT/JP1996/000024 1995-01-11 1996-01-10 Procede permettant de rendre hydrofuge une surface metallique et materiau metallique extremement hydrofuge WO1996021523A1 (fr)

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JP7/2493 1995-01-11
JP249395 1995-01-11
JP7/160590 1995-06-27
JP16059095A JPH08246163A (ja) 1995-01-11 1995-06-27 金属表面への撥液性付与方法

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WO2001056711A1 (fr) 2000-02-03 2001-08-09 Sunyx Surface Nanotechnologies Gmbh Conduite comportant une paroi interieure ultraphobe
US7214302B1 (en) 1999-10-05 2007-05-08 Sunyx Surface Nanotechnologies Gmbh Method and device for moving and placing liquid drops in a controlled manner
US7456392B2 (en) 2002-02-22 2008-11-25 Qiagen Gmbh Use of ultraphobic surfaces having a multitude of hydrophilic areas for analyzing samples
US7632466B2 (en) 2000-02-09 2009-12-15 Qiagen Gmbh Ultraphobic surface structure having a plurality of hydrophilic areas
WO2010017995A1 (fr) 2008-08-15 2010-02-18 Qiagen Gmbh Procédé d'analyse d'un échantillon complexe par spectrométrie de masse
JP2015071552A (ja) * 2013-10-02 2015-04-16 Ａｇｃセイミケミカル株式会社 パーフルオロアルキル基含有リン酸モノエステルの製造方法

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CN1321271C (zh) * 2002-06-27 2007-06-13 旭技术株式会社 表面加工件和表面加工方法及表面加工装置
JP4872182B2 (ja) * 2003-03-06 2012-02-08 日本軽金属株式会社 アルミニウム塗装材及びその製造方法
US7455045B2 (en) 2006-08-01 2008-11-25 Aisan Kogyo Kabushiki Kaisha Fluid flow control device for internal combustion engine
JP6060882B2 (ja) * 2013-12-03 2017-01-18 マツダ株式会社 断熱層形成用のＡｌ合金製エンジン部品表面の処理方法
JP6256264B2 (ja) * 2014-09-05 2018-01-10 Ｊｆｅスチール株式会社 亜鉛系めっき鋼板
JP6498091B2 (ja) * 2015-09-25 2019-04-10 Ｊｘ金属株式会社 表面処理金属箔、積層体、プリント配線板、半導体パッケージ、電子機器
JP2019144335A (ja) * 2018-02-19 2019-08-29 デクセリアルズ株式会社 微細構造体及びその製造方法、並びに光学機器
TW202340531A (zh) * 2022-02-21 2023-10-16 日商三井化學股份有限公司 金屬構件、金屬樹脂接合體及金屬構件之製造方法

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7214302B1 (en) 1999-10-05 2007-05-08 Sunyx Surface Nanotechnologies Gmbh Method and device for moving and placing liquid drops in a controlled manner
WO2001056711A1 (fr) 2000-02-03 2001-08-09 Sunyx Surface Nanotechnologies Gmbh Conduite comportant une paroi interieure ultraphobe
US7632466B2 (en) 2000-02-09 2009-12-15 Qiagen Gmbh Ultraphobic surface structure having a plurality of hydrophilic areas
US7456392B2 (en) 2002-02-22 2008-11-25 Qiagen Gmbh Use of ultraphobic surfaces having a multitude of hydrophilic areas for analyzing samples
WO2010017995A1 (fr) 2008-08-15 2010-02-18 Qiagen Gmbh Procédé d'analyse d'un échantillon complexe par spectrométrie de masse
EP2157432A1 (fr) 2008-08-15 2010-02-24 Qiagen GmbH Procédé d'analyse d'un échantillon complexe par spectrométrie de masse
JP2015071552A (ja) * 2013-10-02 2015-04-16 Ａｇｃセイミケミカル株式会社 パーフルオロアルキル基含有リン酸モノエステルの製造方法

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