JP2013092289A - Super-hydrophobic and oleophobic heat exchanger member, method for manufacturing the same, and heat exchanger manufactured by using them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a super-hydrophobic and oleophobic heat exchanger member which is improved in durability, such as wear resistance and weather resistance, waterdrop repellency, oleophobic, and antifouling properties, in addition to hydrophobic, oleophobic and antifouling functions, to provide a method for manufacturing the same, and to provide a heat exchanger manufactured by using them.SOLUTION: The super-hydrophobic and oleophobic heat exchanger member 10 includes a substrate 14 having a plurality of Kompeito-like projections 11 and a thin film 15a which has hydrophobic, oleophobic and antifouling properties and is bonded to at least part of the surface of the substrate 14 having the Kompeito-like projections 11, wherein each Kompeito-like projection 11 is composed of a first projection 12 having a nearly hemispherical shape and a plurality of second projections 13 each of which is formed in a cone or bamboo shoot shape on a surface of the first projection 12 and has a bottom face diameter smaller than that of the first projection 12.

Description

The present invention relates to a super water / oil repellent heat exchange member, a method for producing the same, and a heat exchanger using the same, and more specifically, a highly durable, water / oil repellent and antifouling coating is formed on the surface. The present invention also relates to a super water / oil repellent heat exchange member, a method for producing the same, and a heat exchanger using them.

In order to impart water repellency, oil repellency and antifouling properties to the surfaces of various members, a solution comprising a fluorocarbon group-containing chlorosilane-based adsorbent and a non-aqueous organic solvent is used for chemical adsorption in the liquid phase. It is already well known that a molecular film-like water- and oil-repellent antifouling chemical adsorption film monomolecular film can be formed (for example, see Patent Document 1).
The manufacturing principle of such a monomolecular film in a solution is to form a monomolecular film by using a dehydrochlorination reaction between active hydrogen such as hydroxyl group on the substrate surface and chlorosilyl group of chlorosilane-based adsorbent. is there.

A heat exchanger for an air conditioner such as a room air conditioner has a structure in which aluminum fins having a thickness of about 0.1 mm are overlapped at intervals of 1 to 2 mm in order to increase the contact area with air. If the water condensed during the cooling operation forms a so-called bridge between the fins or freezes in that state, the ventilation resistance increases and the air conditioning performance decreases. Further, in the heat exchanger for the dehumidifier, when the surface of the cooling fin remains wet with the dew condensation water, the dew condensation performance is lowered and the dehumidification efficiency is lowered. Therefore, for example, in Patent Document 2, a dehumidifying unit configured by closely fixing a cooling fin to a heat absorbing surface of an electronic cooling element and a heat radiating fin to a heat generating surface, a blower unit that circulates air, a suction port, and In a hygroscopic device having a discharge port and a housing that houses the dehumidifying unit and the air blowing unit, a hygroscopic device is proposed in which a film of a water repellent material is formed on the surface of the cooling fin. Since the contact angle of water droplets of condensation that adheres to the cooling fins increases and the surface moves smoothly downward and is easy to drop, the surface of the cooling fins is prevented from getting wet with condensation water and the condensation capacity is increased. Can be kept high.

JP-A-4-132737 JP-A-6-74479

However, in the case where the chemical adsorption film described in Patent Document 1 is applied to a member having a flat surface, the water droplet contact angle is at most about 120 degrees, so that water droplets and dirt can be removed naturally. There was a problem that the water and oil repellency and antifouling property and water separation were insufficient. Further, the chemical adsorption film monomolecular film described in Patent Document 1 has a problem that durability such as wear resistance and weather resistance is poor.

In addition, since the film of the water repellent material formed on the surface of the cooling fin in the hygroscopic device described in Patent Document 2 is made of a fluororesin or the like, it is generally expensive, and is fundamental due to high cost and a decrease in thermal conductivity. There is a concern about performance degradation.

The present invention has been made in view of such circumstances, and is a super water / oil repellent heat exchange member with improved water-repellent (also referred to as water slidability), oil repellency, and antifouling properties, a method for producing the same, and heat using the same. The purpose is to provide an exchanger.

The first aspect of the present invention that meets the above-mentioned object is a substrate having a plurality of confetti-like protrusions on the surface, and a water- and oil-repellent and antifouling thin film bonded to at least a part of the surface of the substrate having the protrusions. The scallop-shaped projections are formed on the surface of the substantially hemispherical first projection as a core and the surface of the first projection, and the diameter of the bottom surface is smaller than the diameter of the first projection. The above-described problems are solved by providing a super water / oil repellent heat exchange member comprising a plurality of conical or bamboo shoot-like second protrusions.
A surface structure having complex irregularities can be formed by bonding and fixing fine particles as cores on the surface of the base material to form first protrusions, and further bonding and fixing the second protrusions on the surface. Therefore, the water / oil repellency / antifouling property can be improved as compared with the case of having a flat surface. In addition, by forming a water- and oil-repellent and antifouling thin film on at least the surface of the confetti-like protrusions, it is possible to impart water repellency, oil repellency and antifouling properties to the surface of a generally hydrophilic substrate.

In the superhydrophobic / oil-repellent heat exchange member according to the first aspect of the present invention, the fine particles, which are spherical or substantially spherical cores, are fused to the surface of the base material or bonded via a binder. One protrusion may be formed.
Since the first fine particles as the core are bonded and fixed to the surface of the base material through fusion or binder, the wear resistance and weather resistance of the surface of the super water / oil repellent heat exchange member can be improved.

In the super water- and oil-repellent heat exchange member according to the first aspect of the present invention, the core fine particle may have a diameter of 30 nm to 10 μm, and the second protrusion may have a height of 10 to 300 nm. .
By doing in this way, the super water-repellent and oil-repellent heat exchange member excellent in water repellency, oil repellency, and antifouling property can be provided.

In the super water- and oil-repellent heat exchange member according to the first aspect of the present invention, even if the height of the second protrusion is 1/10 or more and 1/2 or less of the height of the first protrusion. Good.

In the super water / oil repellent heat exchange member according to the first aspect of the present invention, the second protrusion may be made of zinc oxide.

In the super water / oil repellent heat exchange member according to the first aspect of the present invention, the fine particles may be made of a material selected from the group consisting of glass, silica, alumina, and zirconia.
Since the core fine particles are made of a material selected from the group consisting of glass, silica, alumina, and zirconia, the surface durability of the super water / oil repellent heat exchange member can be improved.

In the super water / oil repellent heat exchange member according to the first aspect of the present invention, the water / oil repellent / antifouling thin film is preferably a monomolecular film.
Since the water / oil repellent / antifouling thin film is a monomolecular film, the thermal conductivity of the obtained super water / oil repellent heat exchange member is not impaired.

In the super water / oil repellent heat exchange member according to the first aspect of the present invention, the lower the critical surface energy of the surface, the better, but it is preferably 1 mN / m or more and 3 mN / m or less.
Since the critical surface energy of the surface is in the above range, all of the water repellency, oil repellency and antifouling property of the obtained super water / oil repellency heat exchange member can be improved.

In the second aspect of the present invention, the step A in which spherical or substantially spherical core particles dispersed in a solvent are sprayed on the surface of the substrate, and the substrate on which the core particles are sprayed is heated. Then, the step B for bonding and fixing the core fine particles to the surface of the substrate to form a substantially hemispherical first protrusion, and the first protrusion on the surface of the first protrusion The step C for forming a plurality of conical or bamboo shoot-like second projections having a bottom diameter smaller than the diameter of the first and second projections is formed. The above-mentioned problem is solved by providing a method for producing a super water / oil / oil repellent heat exchange member characterized by comprising a step D of forming a water / oil / oil repellent / antifouling thin film on the surface of a substrate. .
In Steps A to C, complex irregularities can be formed on the surface of the base material by forming a plurality of confetti-like projections bonded or fused to the surface of the base material. Therefore, the water repellency, oil repellency and antifouling property can be improved as compared with a base material in which only a flat base material and core fine particles are bonded and fixed to the surface. Further, in step C, the water and oil repellency and antifouling properties can be further improved by forming a water and oil repellency and antifouling property thin film on at least the surface of the confetti-like protrusions.

In the method for manufacturing a super water / oil repellent heat exchange member according to the second aspect of the present invention, the height of the scallop-like protrusions may be 30 to 300 nm.

In the above case, it is preferable that the diameter of the core fine particle is 30 nm to 10 μm and the height of the second protrusion is 10 to 300 nm.

In the method for producing a super water- and oil-repellent heat exchange member according to the second aspect of the present invention, in the step B, the base material after the dispersion is applied is not less than the softening point of the base material and the core. The core fine particles may be fused to the surface of the substrate by heating at or below the melting point of the fine particles.

In the method for producing a super water / oil repellent heat exchange member according to the second aspect of the present invention, the dispersion contains a binder precursor that generates a binder by evaporation of a solvent and / or subsequent chemical reaction, In B, the core fine particles may be bonded and fixed or fused to the surface of the base material via the binder.
Since the core fine particles are bonded, fixed, or fused to the surface of the substrate via fusion or a binder, the wear resistance, weather resistance, and the like of the surface of the super water / oil repellent heat exchange member can be improved.

In the method for producing a super water- and oil-repellent heat exchange member according to the second aspect of the present invention in which fine particles serving as cores are bonded and fixed via a binder in Step B, the binder precursor is subjected to metal oxidation by a sol-gel method. The metal sol precursor which forms a thing may be sufficient.
By using a metal sol precursor that forms a metal oxide by a sol-gel method as a binder precursor, the core fine particles can be firmly bonded and fixed to the surface of the substrate.

In the method for manufacturing a super water / oil repellent heat exchange member according to the second aspect of the present invention, after the step B, the core fine particles that are not bonded and fixed may be washed away.

In the method for producing a super water- and oil-repellent heat exchange member according to the second aspect of the present invention, in the step B, the surface of the core fine particles adhered, bonded, or fused to the surface of the base material is used. Preferably, the protrusions made of zinc oxide are formed using an atmospheric pressure plasma method.

In the method for producing a super water- and oil-repellent heat exchange member according to the second aspect of the present invention, in the step D, a reactive group that forms a bond by reacting with a surface functional group of the base material and the confetti-like protrusion. And a reaction solution containing a compound having a fluorocarbon group or a dimethylsilyl group is brought into contact with the surface of the substrate on which the first and second fine particles are bonded and fixed, and the surface functional group and the reactive group You may form the film of the said compound fixed to this surface through the bond formed by reaction.
Durability of water- and oil-repellent antifouling thin film by bonding and fixing the water-repellent and oil-repellent antifouling thin film to the surface of confetti-like protrusions through a bond formed by the reaction between the surface functional group and the reactive group Can be improved.

In this case, the reactive group is an alkoxysilyl group, and the reaction solution is
(1) one or two or more compounds selected from the group consisting of carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters and titanate ester chelates, and / or Alternatively, (2) one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds may be included as a condensation catalyst.
By using an alkoxysilyl group as a reactive group, it is possible to prevent the formation of harmful by-products such as hydrogen halide during the reaction, and the reaction solution contains a condensation catalyst. The processing time required for forming the thin film can be shortened.

Further, after the step C, the excess reaction solution may be removed by washing.
By washing and removing excess reaction liquid, the water / oil / oil / repellency antifouling thin film can be made into a monomolecular film, so that the thermal conductivity of the manufactured super water / oil / oil repellent heat exchange member is not impaired. .

In the method for producing a super water / oil repellent heat exchange member according to the second aspect of the present invention, the step C may be performed before the step B.

The third aspect of the present invention solves the above problem by providing a heat exchanger having the super water / oil repellent heat exchange member according to the first aspect of the present invention.
A heat exchanger excellent in water repellency, oil repellency and antifouling property can be provided.

When the heat exchanger according to the third aspect of the present invention is a heat absorber, the first aspect of the present invention can solve problems such as a decrease in ventilation resistance due to adhesion or freezing of condensed water and a decrease in condensation performance. A heat exchange member can be applied more suitably.

According to the present invention, in addition to the water / oil repellent / antifouling function, super water / oil repellent with improved durability, such as abrasion resistance and weather resistance, water-drop separation (also referred to as water slidability), oil repellency and antifouling properties. An oily heat exchange member and a method for manufacturing the same are provided. Moreover, according to this invention, in addition to water repellency, oil repellency, and antifouling property, the heat exchanger excellent in durability is provided.

It is explanatory drawing which demonstrated typically the cross-section of the super water-oil-repellent heat exchange member which concerns on one embodiment of this invention. It is explanatory drawing of the process of fuse | melting the microparticles | fine-particles used as a core on the surface of a base material in the manufacturing method of the same super water / oil repellency heat exchange member. In the manufacturing method of the super water-repellent and oil-repellent heat exchange member, it is an explanatory view of a step of forming a plurality of conical protrusions on the surface of the core fine particles fused to the surface of the substrate. 2 is a scanning electron microscope (SEM) photograph of the surface of a super water / oil repellent heat exchange member produced in Example 1. FIG.

Next, embodiments of the present invention will be described with reference to the accompanying drawings for understanding of the present invention. 1 to 3 are merely schematic explanatory views, and the size of the compound forming the base material, the first and second protrusions, and the water / oil repellent / antifouling thin film is not necessarily a ratio of the actual size. Does not reflect.
As shown in FIG. 1, the super water / oil repellent heat exchange member 10 according to the first embodiment of the present invention includes a base material 14 on which a plurality of confetti-like protrusions 11 are formed, and a base having the protrusions 11. And a water / oil repellent / antifouling thin film 15a bonded to at least a part of the surface of the material 14a. The confetti-like projections 11 are formed on the surface of a substantially hemispherical first projection 12 as a core and the surface of the first projection 12, and a plurality of conical shapes having a bottom diameter smaller than the diameter of the first projection 12. Or it is comprised by the 2nd protrusion 13 of a bamboo shoot shape.

The super water / oil repellent heat exchange member 10 includes a step A in which spherical or substantially spherical core particles 16 dispersed in a solvent are sprayed on the surface of the substrate 14, and a substrate on which the core particles 16 are sprayed. 14 is heated to bond and fix or fuse the core fine particles 16 to the surface of the base material 14 to form a first hemispherical first protrusion 12, and adhere to and bond to the surface of the base material 14. A plurality of bamboo shoot-like protrusions 13 (an example of a conical or bamboo shoot-like second protrusion: a second protrusion having a conical shape or a bamboo shoot shape) having a bottom surface diameter smaller than the diameter of the first protrusion 12 on the surface of the first protrusion 12 fixed or fused. Hereinafter, the process C is formed simply, and the hemispherical protrusion (an example of the first protrusion) 12 and the bamboo shoot-like protrusion formed by the fused fine particles 16a. A confetti-like protrusion 11 composed of 13 is formed. Produced by the process and a step D of the surface of the substrate 14a to form a water-repellent oil-repellent antifouling film 15a was.
Hereinafter, the processes A to D will be described in more detail.

(1) Process A
There is no restriction | limiting in particular about the shape of the base material 14 used for manufacture of the super water / oil repellent heat exchange member 10, The thing of arbitrary shapes can be used. Specific examples of the shape of the base material 14 include those having an arbitrary shape such as a sheet shape, a corrugated plate shape, a tape shape, a tube shape, a bellows shape, or a sword mountain shape, which are usually used for a heat exchange member. Moreover, there is no restriction | limiting in particular also about the magnitude | size of the base material 14, The thing of arbitrary magnitude | sizes can be used. Furthermore, there is no restriction | limiting in particular also about the material of the base material 14, The thing of arbitrary materials, such as metal materials, such as aluminum, copper, or those alloys, highly heat conductive ceramics, such as silicon nitride and aluminum nitride, can be used.

Before spraying the fine particles 16, it is preferable to clean the surface of the base material 14 and remove dirt adhering to the surface. For the cleaning, any method such as immersion in a cleaning solution (heating, stirring, ultrasonic irradiation or the like may be used in combination), corona treatment, oxygen plasma treatment, or excimer light irradiation can be used.

The fine particles 16 serving as the core used for producing the super water / oil repellent heat exchange member 10 are spherical or substantially spherical, and have a diameter of 10 nm to 5 mm, preferably 20 nm to 50 μm, more preferably 30 nm to 10 μm.

There are no particular restrictions on the material of the fine particles 16 as the core, and any material such as soda lime glass, crystal glass, quartz glass, borosilicate glass, phosphorus glass, boron glass, glass ceramics, silica, alumina, zirconia, or the like is used. Organic materials such as acrylic glass (plexiglass) made of polymethyl methacrylate or the like can also be used. In particular, in the case of using fine particles as the core made of a hard inorganic oxide such as silica, alumina, zirconia, etc., the surface hardness and wear resistance of the resulting super water / oil repellent heat exchange member 10 can be improved. When the base material 14 is a metal having a low melting point such as aluminum and the core fine particles 16 are directly fused to the surface thereof, the melting point of silica or the like is too high, so that the low melting point of phosphorus glass or boron glass or the like is low. It is necessary to use glass.

The dispersion of the fine particles 16 serving as the core can be performed by any method. For example, a method of evaporating the solvent after applying the dispersion liquid in which the fine particles 16 serving as the core are dispersed in the solvent is preferable. Used.
For the preparation of the dispersion, any solvent can be used as long as the fine particles 16 serving as the core can be uniformly dispersed and does not react with the base material 14 and the fine particles 16 serving as the core or cause swelling or deformation. From the viewpoints of volatility, safety, environmental burden, economy, and the like, water, lower alcohol solvents such as ethanol and isopropyl alcohol, and mixed solvents thereof are preferable. Although the amount of the solvent depends on the size and specific gravity of the fine particles 16 serving as the core, it is difficult to uniquely determine. For example, the amount of the solvent is 4 to 200 times the weight of the fine particles 16 serving as the core (first The concentration of the fine particles 16 serving as the core contained in the dispersion is about 0.5 to about 20% by weight), preferably 10 to 100 times, more preferably 10 to 50 times. If the amount of the solvent is too small, the resulting first dispersion becomes a slurry, making it difficult to uniformly disperse the fine particles 16 serving as the core on the surface of the base material 14. Decreases.

When the solvent is evaporated after applying the dispersion on the surface of the base material 14, the fine particles 16 serving as the core can be uniformly dispersed on the surface of the base material 14. For the application of the first dispersion, any method such as a dip coating method, a spin coating method, a spray method, a screen printing method, or the like can be used.

(2) Process B
Next, the surface of the base material 14 on which the fine particles 16 serving as the core are dispersed is heated at a temperature equal to or higher than the softening point of the base material 14 and lower than the melting point of the fine particles 16 serving as the core, so that the fine particles 16 serving as the core melt on the surface. The attached base material 14a is obtained. Although the heating temperature and the heating time depend on the base material 14 used and the material of the fine particles 16 serving as the core, it is difficult to uniquely determine. For example, for example, aluminum (silica described later) is used as the base material 14. A coating may be formed on the surface.) When silica fine particles are used as the fine particles 16, the core fine particles 16 are fused to the surface by heating at 650 ° C. for about 30 minutes to 1 hour, The base material 14b in which the core fine particles are fused is obtained.

The dispersion may contain a binder precursor that generates a binder that can be bonded to the surface of the substrate 14 and the fine particles 16 serving as the core by evaporation of the solvent and / or subsequent chemical reaction. As the binder precursor, for example, one or a plurality of compounds that generate an organic or inorganic polymer by a chemical reaction can be used. Specific examples thereof include (1) a thermosetting resin or a precursor thereof, (2 ) A photocurable resin or a precursor thereof; and (3) a substance capable of forming a metal oxide film by a sol-gel method. Specific examples of the precursor of the thermosetting resin and the precursor of the photocurable resin include an epoxy adhesive, a cyanoacrylate adhesive, and the like, and a substance capable of forming a metal oxide film by a sol-gel method. As specific examples, tetraalkoxysilane Si (OR) ₄ (R is a lower alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, etc .; the same shall apply hereinafter), boric acid trialkoxide B ( OR) ₃ , aluminum trialkoxide Al (OR) ₃ , metal alkoxides such as titanium tetraalkoxide Ti (OR) ₄ , and mixtures thereof.

When the solvent is evaporated after applying the dispersion on the surface of the base material 14, a silica film formed on the surface of the base material 14 by a sol-gel method (hereinafter sometimes referred to as “silica film”). Thus, the fine particles 16 serving as the core can be bonded and fixed in a uniformly dispersed state. In this case, a silica coating may also be formed on the surface of the fine particles 16 serving as the core as long as the shape of the fine particles 16 serving as the core is not impaired and the size is within a desired range. A solution containing a binder precursor is prepared separately from the dispersion, and after the binder precursor solution is applied, the solvent is evaporated to disperse the binder 14 without the binder precursor on the surface of the substrate 14 on which the silica film has been formed in advance. A liquid may be applied.

Next, when the heat treatment at about 200 to 500 ° C. is further performed to sinter the silica coating, the fine particles 16 serving as the core can be bonded and fixed to the surface of the base material 14 more firmly. When the sintering temperature is increased to such an extent that the base glass is softened, the silica coating is melted or softened, and the fine particles 16 serving as the core can be fused. At this time, if phosphoric acid or boric acid of about 5% of the metal alkoxide is added to the dispersion, the melting point of the silica coating can be lowered to about 500 ° C., so that the base glass is softened. The fine particles 16 serving as the core can be fused to the surface of the base material 14 by sintering at 500 to 600 ° C. for about 30 minutes.

Even when either the base material 14 or the core fine particle 16 is an organic material, it is possible to perform bonding and fixing by fusion within a range in which heat resistance can be ensured. However, since the organic material has a lower melting point and softening temperature than the inorganic material and easily undergoes thermal decomposition, the heating temperature needs to be lower than that of the inorganic material.

In the present embodiment, the base material 14 is used as it is for the production of the base material 14b in which the core fine particles are fused in the steps A and B, but the temperature is lower than that of the base material 14 before the step A. Then, a film for fusing the fine particles 16 as the core may be formed on the surface of the substrate 14. As the coating, any coating capable of fusing the core fine particles 16 at a temperature lower than that of the substrate 14 can be used, but a metal oxide such as silicon oxide or aluminum oxide formed by a sol-gel method can be used. The dry gel film is preferred.

When a solution of a metal alkoxide containing a condensation catalyst (details will be described later) is applied to the surface of the substrate 14 and then the solvent is evaporated, hydroxyl groups and alkoxyl groups generated by hydrolysis of the alkoxyl groups by moisture in the air A condensation reaction takes place between them, and a dry gel film of metal oxide is formed on the surface of the substrate 14. Since there are more free hydroxyl groups than the base material 14 on the surface and inside of the unsintered dry gel film, it can be fused to the fine particles 16 at a temperature lower than that of the base material 14.

The formation of a dry gel film of silica, which is an example of the coating, is performed by applying a sol solution obtained by mixing a tetraalkoxysilane such as tetramethoxysilane (Si (OCH ₃ ) ₄ ), a condensation catalyst and a solvent to the surface of the substrate 14. It can be performed by applying and evaporating the solvent.
Condensation catalysts, cocatalysts, solvent types, tetraalkoxysilane concentrations, and catalyst addition amounts that can be used will be described later.

The sol solution can be applied by an arbitrary method such as a dip coating method, a spin coating method, a spray method, an ink jet method, or a screen printing method. Moreover, although the film thickness of a dry gel film is based also on the diameter of the microparticle 16 used as the core used for manufacture of the super water-repellent oil-repellent heat exchange member 10, 5-50 nm is preferable. When the super-water / oil-repellent heat exchange member 10 is manufactured using the base material 14 having a silica dry gel film on the surface thus obtained, the heat treatment in the step A is performed at a low temperature of 300 ° C. or less. It becomes possible. Therefore, even when the air-cooled and strengthened base material 14 is used, it is possible to produce the base material 14b in which the core fine particles are fused without deteriorating the strengthening degree by heating at a high temperature.

As the binder, in addition to an organic or inorganic polymer formed by a chemical reaction, for example, a sprayed coating can be used. In this case, for example, a sprayed coating is formed by spraying atomized powder of the coating material onto the surface of the base material 14 in which the fine particles 16 serving as the core are dispersed.

Process C
Next, a plurality of conical or bamboo shoots having a bottom diameter smaller than the diameter of the core fine particle 16 on the surface of the core fine particle 16 (or 16a) attached, bonded, fixed or fused to the surface of the substrate 14 A protrusion 13 is formed. For the formation of the protrusions 13, a chemical vapor deposition (CVD) method of zinc oxide using an atmospheric pressure plasma method is preferably used from the viewpoint of productivity, ease of enlargement, and the like. For forming the projections 13 made of zinc oxide using the plasma CVD method, a linear plasma torch can be used, a zinc complex or an organic zinc compound can be used as a zinc source, and helium, argon, or the like can be used as a carrier gas. Specific examples of the zinc complex or metal zinc compound include diethyl zinc (Zn (C ₂ H ₅ ) ₂ ), bisacetylacetonate zinc (Zn (acac) ₂ ), bis (2-methoxy-6-methyl-3, 5-heptanedionate) zinc (Zn (MOPD) ₂ ) and the like.

The protrusion 13 formed in this way has a conical or bamboo shoot shape, and the diameter of the bottom surface is, for example, 1/100 or more and 1/5 or less of the diameter of the fused fine particles 16a. 1 nm to 50 μm, preferably 5 nm to 80 nm, more preferably 10 to 20 nm. The aspect ratio of the protrusion 13 defined by the ratio of the height of the protrusion 13 to the diameter of the bottom surface of the protrusion 13 is, for example, 1 or more and 5 or less. If the aspect ratio is too large, the second protrusions 23 are likely to break, and if the aspect ratio is too small, the surface shape of the manufactured super water / oil repellent heat exchange member 10 is reduced in fractal nature. Water repellent and oil repellent antifouling performance is less likely to be exhibited.

Note that, as shown in FIG. 3, bamboo shoot-like projections 13 may be formed on the surface of the base material 14. Here, even if the process C is performed before the process B, a similar surface shape can be formed.

Process D
Water / oil / oil repellent and bonded to the surface of the substrate 14a on which the surface of the base 14a on which the gold-peel-like projections (11) are formed is bonded and fixed through a bond formed by a reaction between a surface functional group (not shown) and a surface reactive group. The reaction liquid used to form the dirty thin film 15a and produce the super water / oil repellent heat exchange member 10 is an alkoxysilane compound containing a fluorocarbon group (a film compound having a surface reactive group and a fluorocarbon group). 15), a condensation catalyst for accelerating the condensation reaction between a hydroxyl group (an example of a surface functional group) on the surface of the base material 14a on which the confetti-like protrusions (11) are formed and an alkoxysilyl group, It is prepared by mixing with an aqueous organic solvent.

Examples of the alkoxysilane compound containing a fluorocarbon group include alkoxysilane compounds represented by the following general formula (I).

_{(I) CF 3 (CF 2} ) n -Y-Z- (CH 2) m -Si (OR) 3

In the above formula, m represents an integer of 0 to 20, n represents an integer of 0 to 9, and R represents an alkyl group having 1 to 4 carbon atoms.
Y represents (CH ₂ ) _k (k represents an integer of 1 to 3) and a single bond, and Z represents O (ether oxygen), COO, Si (CH ₃ ) ₂ , and a single bond. Represents one of the bonds.

Examples of the alkoxysilane compound containing a fluorocarbon group represented by the formula (I) include compounds shown in the following (1) to (12).

(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(2) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(3) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(4) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(5) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(7) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(8) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(9) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(10) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
(11) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(12) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃

As the condensation catalyst, metal salts such as carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters and titanate ester chelates can be used.
The addition amount of the condensation catalyst is preferably 0.2 to 5% by mass of the alkoxysilane compound, and more preferably 0.5 to 1% by mass.

Specific examples of carboxylic acid metal salts include stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, naphthenic acid Lead, cobalt naphthenate, and iron 2-ethylhexenoate.

Specific examples of the carboxylic acid ester metal salt include dioctyltin bisoctylthioglycolate ester salt and dioctyltin maleate ester salt.
Specific examples of the carboxylic acid metal salt polymer include dibutyltin maleate polymer and dimethyltin mercaptopropionate polymer.
Specific examples of the carboxylic acid metal salt chelate include dibutyltin bisacetylacetate and dioctyltin bisacetyllaurate.

Specific examples of the titanate ester include tetrabutyl titanate and tetranonyl titanate.
Specific examples of titanate chelates include bis (acetylacetonyl) dipropyl titanate.

When a reaction solution is applied to the surface of the base material 14a on which the confetti protrusions (11) are formed and reacted in air at room temperature, the base material 14a on which the alkoxysilyl groups and the confetti protrusions (11) are formed. The surface hydroxyl group undergoes a condensation reaction to produce a water- and oil-repellent and antifouling thin film 15a containing a fluorocarbon group having a structure as shown in Chemical Formula 1 below. The three single bonds extending from the oxygen atom are bonded to the hydroxyl group on the surface of the base material 14a on which the confetti-like projections (11) are formed or to the silicon (Si) atom of the adjacent silane compound, At least one is bonded to the hydroxyl group on the surface of the base material 14a on which the confetti-like protrusions (11) are formed.

Since the alkoxysilyl group decomposes in the presence of moisture, the reaction is preferably performed in air with a relative humidity of 45% or less. The condensation reaction is inhibited by the oil and fat adhering to the surface of the base material 14a on which the confetti-like projections (11) are formed, so that the base material 14a on which the confetti-like projections (11) are formed is removed. It is preferable to remove these impurities in advance by thoroughly washing and drying.
When any of the above metal salts is used as the condensation catalyst, the time required for completion of the condensation reaction is about 2 hours.

When one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are used as the condensation catalyst instead of the above metal salts, Time can be shortened to about 1/2 to 2/3.

Alternatively, when these compounds are used as a co-catalyst and mixed with the above-described metal salt (mass ratio 1: 9 to 9: 1 can be used, preferably around 1: 1), the reaction time is further shortened. it can.

For example, when H3 from Japan Epoxy Resin Co., which is a ketimine compound, is used as the condensation catalyst instead of dibutyltin oxide and the other conditions are the same, the reaction time can be reduced to about 1 hour.

Furthermore, using a mixture of H3 and dibutyltin bisacetylacetonate from Japan Epoxy Resin (mixing ratio is 1: 1) as the condensation catalyst, the reaction time is shortened to about 20 minutes when the other conditions are the same. it can.

The ketimine compound that can be used here is not particularly limited, and examples thereof include 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza- 3,10-tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-penta Decadiene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza -4,19-trieicosadiene and the like.

The organic acid that can be used is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, and malonic acid.

For the preparation of the reaction solution, an organic chlorine solvent, a hydrocarbon solvent, a fluorocarbon solvent, a silicone solvent, and a mixed solvent thereof can be used. In order to prevent hydrolysis of the alkoxysilane compound, it is preferable to remove water from the desiccant or the solvent used by distillation. Moreover, it is preferable that the boiling point of a solvent is 50-250 degreeC.

Specific usable solvents include non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, and alkyl-modified silicone. , Polyether silicone, dimethylformamide and the like.
Furthermore, alcohol solvents such as methanol, ethanol, propanol, or a mixture thereof can also be used.

Fluorocarbon solvents that can be used include fluorocarbon solvents, Fluorinert (manufactured by 3M, USA), Afludo (manufactured by Asahi Glass Co., Ltd.), and the like. In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Furthermore, an organic chlorine solvent such as dichloromethane or chloroform may be added.

The preferable density | concentration of the alkoxysilane compound in a reaction liquid is 0.5-3 mass%.

After the reaction, the substrate is washed with a solvent to remove excess alkoxysilane compound and condensation catalyst remaining on the surface as unreacted materials, and then the surface is covered with a water / oil / oil / oil repellent thin film 15a. The member 10 is obtained.

As the cleaning solvent, any solvent that can dissolve the alkoxysilane compound can be used, but dichloromethane, chloroform, N-methylpyrrolidone, etc. that are inexpensive, have high solubility, and can be easily removed by air drying are preferable. .

After the reaction, if the excess reaction solution is left in the air without being washed away with a solvent, a part of the alkoxysilane compound remaining on the surface is hydrolyzed by moisture in the air, and the generated silanol group becomes an alkoxysilyl group. Causes a condensation reaction. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the super water / oil repellent heat exchange member 10. This polymer film is not fixed to the surface of the super water / oil repellent heat exchange member 10 by a covalent bond, but has water and oil repellent / antifouling properties because it has a fluorocarbon group. Therefore, it can be used as the super water / oil repellent heat exchange member 10 in this state as long as the durability is somewhat inferior.

Although the case where an alkoxysilane compound is used has been described in this embodiment mode, a halosilane compound having a fluorocarbon group may be used. When a halosilane compound is used, a condensation catalyst and a cocatalyst are not required, an alcohol solvent cannot be used, and it is more susceptible to hydrolysis than an alkoxysilane compound. The reaction solution can be prepared and the reaction with the base material 14a on which the confetti-like protrusions (11) are formed can be performed in the same manner as the alkoxysilane compound.

Since the film thickness of the monomolecular water-repellent / oil-repellent antifouling thin film 15a is about 1 nm at most, it is about 5 to 50 nm formed on the surface of the base material 14a on which the confetti-like projections (11) are formed. The unevenness is hardly damaged. In addition, due to this unevenness effect (so-called “lotus leaf effect”), the apparent surface energy of the super water / oil repellent heat exchange member 10 can be reduced, and the water droplet contact angle is 140 ° or more (in this embodiment). About 150 °) and super water-repellent properties can be realized.

Moreover, as a halosilane compound containing the fluorocarbon group which can be used in the process D, the compound shown to following (21)-(26) is mentioned. Moreover, the isocyanate silane compound shown to following (27)-(32) can also be used.

(21) CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃
(22) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ SiCl ₃
(23) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃
(24) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃
(25) CF ₃ COO (CH ₂ ) ₁₅ SiCl ₃
(26) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃
(27) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (NCO) ₃
(28) CF ₃ (CH ₂ ) ₃ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (NCO) ₃
(29) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (NCO) ₃
(30) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (NCO) ₃
(31) CF ₃ COO (CH ₂ ) ₁₅ Si (NCO) ₃
(32) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (NCO) ₃

The super water / oil repellent heat exchange member 10 has a water droplet contact angle of about 150 degrees. From the study results using various volumes of water droplets (0.02 to 0.08 mL), it was confirmed that when the water droplet contact angle is 150 degrees or more, the falling angle is 15 degrees or less regardless of the volume of the water droplet. Yes. Therefore, when the super water / oil repellent heat exchange member 10 is used as a window glass plate for a vehicle or a building, most water droplets cannot fall on the surface and fall down.

The super water and oil repellent heat exchange members 10 and 100 are excellent in durability such as abrasion resistance and weather resistance, water droplet water separation (slidability), and antifouling properties, and require water and oil repellent and antifouling functions. It can be used as a heat exchange member of a heat exchanger. Heat exchangers that can use the super water / oil repellent heat exchange members 10 and 100 include cooling fins for air-cooled engines such as automobiles, railway vehicles, ships, and airplanes, radiators for water-cooled engines, and air conditioners such as room air conditioners. Examples include heat exchangers, household or commercial refrigerators or freezer heat exchangers, and dehumidifier heat exchangers. In particular, super-water / oil-repellent heat exchange for heat sinks and dehumidifiers for air conditioners, refrigerators, and freezers, which are likely to be contaminated with contaminants such as dust, increase airflow resistance due to condensation, and reduce condensation performance. When the members 10 and 100 are applied, since the water droplet contact angle is large, the dew condensation water becomes water droplets and easily falls off the surface. Therefore, an increase in ventilation resistance due to condensation and a decrease in dehumidification efficiency due to a decrease in condensation performance can be greatly reduced.

Next, examples carried out for confirming the effects of the present invention will be described. These examples are illustrative only and are not intended to limit the scope of the invention.
Example 1: Production of super water / oil repellent heat exchange member (1)
[1] Fusion of silica fine particles as a core to the substrate surface A sol-gel solution (silica concentration 2%) prepared by adding a trace amount of water and phosphoric acid to a methanolic solution of tetramethoxysilane is applied to the surface of the aluminum plate. After coating, the film was dried to form a silica film having a film thickness of about several nanometers. Silica fine particles having an average diameter of about 130 nm are dispersed in ethanol, applied to the entire surface of the silica coating, ethanol is evaporated, and further sintered at 600 ° C. for 30 minutes, and then the silica fine particles not fused to the surface are washed. Removed.

At this time, if phosphoric acid or boric acid is added to the above sol-gel solution in a solid content of about 5%, the melting point of the silica coating can be reduced to about 450 ° C., so about 500 minutes at 500 to 600 ° C. The silica fine particles could be sufficiently fused at the sintering temperature. Further, the unevenness derived from the fused composite fine particles was not impaired under these heating conditions.

[2] Second protrusion-forming bis (2-methoxy-6-methyl-3,5-heptanedionate) zinc ((Zn (MOPD) ₂ (C ₁₈ H ₃₀ O ₆ Zn), Ube Industries) by atmospheric pressure plasma Bamboo-like protrusions made of zinc oxide were formed on the surface of an aluminum plate fused with silica fine particles (by means of atmospheric pressure plasma method using helium as a plasma gas) (see FIG. 4). Here, the conditions of the atmospheric pressure plasma method were as follows.
Vaporizer temperature 100 ° C
Substrate temperature 210 ° C
Plasma He gas flow rate 1400ccm
Carrier He gas flow rate 250ccm
Total He gas flow 1650ccm
Oxygen flow rate 50ccm
Gap (gap between cathode electrode and substrate) 0.5mm
Power supply High frequency pulse power supply Applied voltage 1kV
Frequency 20kHz
Stage moving speed 1mm / s (reciprocating motion between 20mm)
Deposition time 180min

[3] Formation of water / oil / oil repellent antifouling film 99 parts by weight of heptadecafluorodecyltrimethoxysilane CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , 1 part by weight of dibutyltin diacetylacetate After each weighed the natto (condensation catalyst), it was dissolved in hexamethyldisiloxane to prepare a reaction solution having a concentration of about 1% by weight. The reaction solution was applied to the surface of the base material to which the fused composite fine particles were fused, and reacted at room temperature. At this time, since the surface of the fused composite fine particles and the silica coating contains a large number of hydroxyl groups, the heptadecafluorodecyltrimethoxysilane-Si (OCH ₃ ) group and the hydroxyl group are removed in the presence of the condensation catalyst. Alcohol (in this case, de-CH ₃ OH) reacts to form a bond as shown in the following chemical formula (Chemical Formula 2), and the water- and oil-repellent and antifouling thin film containing a fluorocarbon group is chemically bonded to the surface. The film was formed in a thickness of about 1 nanometer.

After that, the excess reaction solution is washed and removed with dichloromethane, and then the water and oil repellent, covered with a water and oil repellent and antifouling thin film (monomolecular film) containing fluorocarbon groups chemically bonded to the surface over the entire surface. A super-water / oil-repellent heat exchange member having antifouling properties could be produced. FIG. 4 shows a scanning electron microscope (SEM) photograph of the surface of the super water / oil repellent heat exchange member thus obtained. In FIG. 4, “Sample A” and “Sample B” are photographs taken from different photographing angles for the same super water / oil repellent heat exchange member. As the fused composite fine particles are fused to the surface of the base material and the first silica fine particles, respectively, complex irregularities are formed on the surface. As will be described later, the surface of the flat base material is water and oil repellent. It was confirmed that a water droplet contact angle of 160 ± 4 degrees excellent in water repellency, oil repellency and antifouling property can be realized as compared with a water droplet contact angle of about 110 degrees when the antifouling thin film is formed.

Note that the higher the firing temperature at the time of fusion of the silica fine particles is 250 ° C. or more and lower than the softening temperature of the substrate, the stronger the fine particles can be fused to the glass surface. Silica fine particles have been buried inside the material. Therefore, the heating temperature must be about the softening degree of the substrate or less.

On the other hand, at this time, the formed water- and oil-repellent and antifouling thin film on the surface of the fine particles has the effect of reducing the surface energy of the silica fine particles, and the apparent surface of the substrate surface along with the unevenness having a fractal structure. It has the effect of greatly reducing energy. When the water drop contact angle was actually measured, although some variation was observed, the contact angle was about 160 ° and the critical surface energy was about 1 to 3 mN / m.

[4] Evaluation of water repellency performance The aluminum plate having super water and oil repellency obtained in this way is mounted on a Peltier element (for 12V, 4 cm x 4 cm, 3.82 mm thickness), and the Peltier element is energized. The heat sink was cooled, and a dew condensation test (in air at room temperature, relative humidity 55%) was performed. As a result, the condensed water droplets became spherical without conforming to the surface of the sheet sink, and easily dropped off the surface by ventilating with a fan or tilting the heat sink.

Example 2: Production of super water / oil repellent heat exchange member (2)
Implementation was performed except that two types of silica fine particles having different diameters (silica fine particles having an average diameter of 50 nm and silica fine particles having an average diameter of 10 nm were mixed and used in a ratio of about 1:10) were used as the fine particles serving as the core of the confetti-like protrusions. In the same manner as in Example 1, confetti-like protrusions were formed on the surface of the aluminum plate. After that, when a water- and oil-repellent and antifouling thin film containing a fluorocarbon group is formed on the surface on which the confetti-like protrusions are formed, the cross section near the surface has a fractal structure and a high water and oil repellent effect (with a water droplet contact angle). An aluminum plate covered with a film (158 degrees) could be produced. A cooling test using a Peltier device was performed in the same manner as in Example 1, and it was confirmed that the same water repellency performance as in Example 1 was exhibited.

Example 3 Production of Super Water / Oil Repellent Heat Exchange Member (3)
Using the same method as in Example 1, a heat absorbing fin for a dehumidifier having a water / oil repellent / antifouling antireflective coating formed thereon was produced and attached to the dehumidifier for testing. Since the numerical value of the relative humidity in the atmosphere was kept almost constant for a long time, no significant decrease in the dew condensation performance due to the retention of the dew condensation water on the endothermic fin surface was confirmed.

DESCRIPTION OF SYMBOLS 10 Super water- and oil-repellent heat exchange member 11 Kinpe sugar-like protrusion 12 Hemispherical protrusion 13 Bamboo-like protrusion 14 Base material 14a Base material 14b with gold-peel-like protrusion formed Base material in which core fine particles are fused 15 Compound having surface reactive group and fluorocarbon group 15a Water- and oil-repellent and antifouling thin film 16 Core fine particle 16a Core fine particle fused to base material

Claims (22)

A substrate having a plurality of confetti-like protrusions on the surface;
A water- and oil-repellent and antifouling thin film bonded to at least a part of the surface of the substrate having the protrusions;
The confetti-shaped projections are formed on a substantially hemispherical first projection comprising fine particles as a core and on the surface of the first projection, and a plurality of bottom diameters smaller than the diameter of the first projection. A super-water / oil-repellent heat exchange member characterized by comprising a conical or bamboo shoot-like second protrusion. 2. The ultrathin shape according to claim 1, wherein the first protrusion is formed by fusing a fine particle serving as a spherical or substantially spherical core to the surface of the base material or bonding the fine particle through a binder. Water / oil repellent heat exchange member. The diameter of the core fine particles is 30 nm to 10 μm,
The super water / oil repellent heat exchange member according to claim 2, wherein the height of the second protrusion is 10 to 300 nm. 4. The super water / oil repellent heat exchange member according to claim 1, wherein the height of the second protrusion is 1/10 or more and 1/2 or less of the height of the first protrusion. 5. The super water / oil repellent heat exchange member according to claim 1, wherein the second protrusion is made of zinc oxide. The super-water / oil-repellent heat according to any one of claims 1 to 5, wherein the core fine particles are made of a material selected from the group consisting of glass, silica, alumina, and zirconia. Replacement member. The super water / oil repellent heat exchange member according to any one of claims 1 to 6, wherein the water / oil repellent / antifouling thin film is a monomolecular film. The super-water / oil-repellent heat exchange member according to any one of claims 1 to 7, wherein the surface has a critical surface energy of 1 mN / m or more and 3 mN / m or less. A step A of dispersing fine particles, which are the cores of spherical or substantially spherical cores dispersed in a solvent, onto the surface of the substrate;
The base material on which the core particles serving as the core are dispersed is heated so that the core particles serving as the core are bonded and fixed or fused to the surface of the substrate to form a substantially hemispherical first protrusion. Forming step B;
Forming a plurality of conical or bamboo shoot-like second protrusions having a bottom diameter smaller than the diameter of the first protrusion on the surface of the first protrusion; and
And a step D of forming a water- and oil-repellent and antifouling thin film on the surface of the base material on which the confetti-like projections composed of the first and second projections are formed. A method for producing a water / oil repellent heat exchange member. The method for producing a super-water / oil-repellent heat exchange member according to claim 9, wherein the height of the confetti-like protrusion is 30 to 300 nm. 11. The method for producing a super water / oil repellent heat exchange member according to claim 10, wherein the core fine particles have a diameter of 30 nm to 10 μm, and the second protrusions have a height of 10 to 300 nm. In the step B, the base material after the dispersion is applied is heated at a temperature equal to or higher than the softening point of the base material and below the melting point of the core fine particles, and the core fine particles are melted on the surface of the base material. The method for producing a super water / oil repellent heat exchange member according to claim 9, wherein the heat exchange member is worn. The dispersion contains a binder precursor that generates a binder by evaporation of the solvent and / or subsequent chemical reaction, and in the step B, the core fine particles are bonded and fixed to the surface of the base material via the binder. The method for producing a super water / oil repellent heat exchange member according to claim 9, wherein the heat exchange member is fused. The method for producing a super water / oil repellent heat exchange member according to claim 13, wherein the binder precursor is a metal sol precursor that forms a metal oxide by a sol-gel method. The super water / oil repellent heat exchange member according to any one of claims 9 to 14, wherein after the step B, the core fine particles which have not been fixed or fused are washed and removed. Production method. In the step B, the projections made of zinc oxide are formed on the surface of the core fine particles adhered, bonded, or fused to the surface of the base material using an atmospheric pressure plasma method. The method for producing a super water / oil repellent heat exchange member according to any one of claims 9 to 15. In the step D, a reaction solution containing a compound having a reactive group that reacts with a surface functional group of the base material and the confetti-like protrusion to form a bond and a fluorocarbon group or a dimethylsilyl group is used. And a surface of the base material on which the second protrusion is formed, and a film of the compound bonded and fixed to the surface is formed through a bond formed by a reaction between the surface functional group and the reactive group The method for producing a super water- and oil-repellent heat exchange member according to any one of claims 9 to 16. The reactive group is an alkoxysilyl group, and the reaction solution is
(1) one or more compounds selected from the group consisting of carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters and titanate ester chelates, and / or Or (2) one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds as a condensation catalyst. 18. A method for producing a super water / oil repellent heat exchange member according to item 17. 19. The method for producing a super water / oil / oil repellent heat exchange member according to claim 17 or 18, wherein after the step C, the excess reaction solution is washed away. The method for producing a super water / oil repellent heat exchange member according to any one of claims 9 to 19, wherein the step C is performed before the step B. A heat exchanger comprising the super water / oil repellent heat exchange member according to claim 1. The heat exchanger according to claim 21, wherein the heat exchanger is a heat absorber.