RU2232648C2 - Superphobic surface - Google Patents

Abstract

FIELD: structured surface with superphobic properties and methods of creation thereof.

SUBSTANCE: superphobic surface has topography which is characterized by relation between spatial frequencies of individual Fourier components and their amplitudes a(f) which are determined from function S: S(log f)=a(f)•f. Integral of the function calculated between lower limit of log(f₁/μm^-1)= -3 and upper limit of log(f₂/μm^-1)=3 is at least 0.5. The surface if made of hydrophobic or mainly of oleophilic material or have covering of hydrophobic or mainly of oleophilic material.

EFFECT: possibility of performing superphobic test of materials with different surface structure, possibility of surface self-cleaning, elimination of manufacturing new negative with demanded topography of superphobic surface.

26 cl, 6 dwg, 1 tbl

Description

The present invention relates to an ultra-phobic surface, to a method for its preparation and its use. The topography of this surface is characterized by the fact that the relationship between the spatial frequencies f of the individual Fourier components and their amplitudes a (f) is determined by the function S

whose integral, calculated between the lower limit of integration log (f ₂ / μm ^-1 ) = - 3 and the upper limit of integration log (f ₂ / μm ^-1 ) = 3, is at least 0.5, and that said surface is made of hydrophobic or especially oleophobic material or has a coating of such a hydrophobic or especially oleophobic material.

A distinctive feature of ultra-phobic surfaces is that the wetting angle of a drop of liquid, usually of water on the surface, significantly exceeds 90 °, and the rolling angle does not exceed 10 °. Ultra-phobic surfaces with a contact angle> 150 ° and the aforementioned rolling angle are of extremely important technical importance, since they are not wetted, for example, with water, nor with oil, dirt particles have only the smallest adhesion to these surfaces, and these surfaces are self-cleaning. In this case, self-cleaning is understood as such a property of the surface in which adhering particles of dirt or dust can easily be washed off with a fluid stream.

With this in mind, numerous attempts have been made to create surfaces with such ultra-phobic properties. So, in particular, in the application EP 476510 A1 describes a method of producing an ultraphobic surface, in which a film of metal oxide is applied to a glass surface, and then it is treated by etching using a plasma discharge in argon (Ar-plasma). The disadvantage of the surfaces obtained by this method is that the contact angle of the droplet located on such a surface is less than 150 °.

US Pat. No. 5,693,236 also describes several methods for producing ultrafobic surfaces, according to which microneedles of zinc oxide are applied to the surface using an appropriate binder, after which they are partially exposed in various ways (for example, by plasma treatment). Then, a surface made of a water-repellent is applied to the surface so structured. However, even with this approach, structured (profiled) surfaces with a contact angle not exceeding 150 ° are obtained.

WO 96/04123 also discloses methods for producing ultrafobic surfaces. According to the technical solution proposed in this application, the profile of the required surface is obtained already in the manufacture of the corresponding molded product from hydrophobic polymers by using forms for this purpose, the inner surface of which is a negative (i.e., back print) of the desired surface profile. However, this approach also has the disadvantage that before forming the product with the required surface profile, it is necessary to produce a negative with such a profile. In addition, in the manufacture of this form with a reverse imprint, the probability of occurrence of defects in the surface, which then after the impression from the negative, i.e. receiving "positive" from a hydrophobic polymer will adversely affect the surface properties.

Based on the foregoing, the present invention was based on the task of obtaining surfaces with ultra-phobic properties and to develop a method for producing such surfaces with a wetting angle of ≥150 ° and preferably with a rolling angle of ≤10 °.

The term "rolling angle" in the context of the present description refers to the angle of inclination of a generally flat and at the same time profiled surface relative to the horizontal at which a fixed drop of water with a volume of 10 μl when tilting the surface begins to slide off it under the action of its own gravity.

A particular problem in this case, as is evident from the above examples, is that the ultraphobic properties of surfaces manifest themselves in different ways. This is due to the fact that the surfaces are made of a wide variety of materials, and in most cases they have a different structure. To date, there is no way that would allow to determine the ultrafobic properties of surfaces regardless of the material from which they are made. Another objective of the invention in accordance with this is the development of a method by which it would be possible to test surfaces for their ultrafobic properties, regardless of the material from which they are made.

This problem is solved according to the invention thanks to a suitably profiled surface with ultra-phobic properties, which is characterized in that it is characterized by a topography in which the integral of the function S

establishing the relationship between the spatial frequencies f of the individual components of the Fourier series and their amplitudes a (f), calculated between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration log (f ₂ / μm ^-1 ) = 3 is at least 0.5, and the surface itself is made of a hydrophobic or primarily oleophobic material or has a coating of such a hydrophobic or primarily oleophobic material.

The hydrophobic material is, according to the invention, a material whose contact angle with water on a flat, non-profiled surface exceeds 90 °.

The oleophobic material is, according to the invention, a material whose contact angle of contact with long chain n-alkanes, such as n-decane, on a flat, non-profiled surface exceeds 90 °.

Preferably, said integral of function (1) is greater than 0.6.

An ultra-phobic surface is preferred whose contact angle with water is at least 150 °, in particular at least 155 °.

The ultra-phobic surface or its substrate is expediently made of metal, plastic, glass or ceramic. Particularly preferred is a metal selected from the group consisting of beryllium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhenium, palladium , silver, cadmium, indium, tin, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum , gold, thallium, lead, bismuth, primarily titanium, aluminum, magnesium and nickel or the corresponding alloy OF DATA metals. The most preferred metal for producing an ultra-phobic surface is an alloy of aluminum and magnesium, especially A1Mg ₃ .

As a plastic material for an ultraphobic surface or its substrate, it is preferable to use duroplastics or thermoplastics. It is advisable to choose Duroplast primarily from the group including diallyl phthalate resin, epoxy resin, urea-formaldehyde resin, melamine-formaldehyde resin, melamine-phenol-formaldehyde resin, phenol-formaldehyde resin, polyimide, silicone rubber and unsaturated resin. It is advisable to choose a thermoplastic primarily from the group comprising a thermoplastic polyolefin, for example polypropylene or polyethylene, polycarbonate, polyester carbonate, polyesters, for example PBT or PET, polystyrene, styrene copolymer, styrene-acrylonitrile copolymer, rubber grafted acrylic copolymer, styrene copolymer copolymer, styrene (ABS plastic), polyamide, polyurethane, polyphenylene sulfide, polyvinyl chloride or any possible mixture of these polymers.

The following thermoplastic polymers are particularly suitable as a substrate for a surface according to the invention:

polyolefins, such as high and low density polyethylene, i.e. with a density of from 0.91 to 0.97 g / cm ³ which can be obtained by known methods (see Ullmann, 4th edition, 19, p. 166 onwards; Winnacker-Kuchler, 4th edition, 6, p. .353-367; Elias and Vohwinkel, Neue Polymere Werkstoffe fur die industrielle Anwendung, Munchen, Hanser Verlag (1983)).

In addition to the above, polypropylenes with a molecular weight of from 10,000 to 1,000,000 g / mol are suitable, which can be obtained by known methods (see Ullmann, 5th edition, A10, p. 615 onwards; Houben-Weyl E 20/2, p. 722 farther; Ullmann, 4th edition, 19, p. 95 ff; Kirk-Othmer, 3rd edition, 16, p. 357 ff).

It is also possible to use copolymers of these olefins or copolymers with other α-olefins, such as, for example, copolymers of ethylene with butene, hexene and / or octene, a copolymer of ethylene and vinyl acetate, a copolymer of ethylene and ethyl acrylate, a copolymer of ethylene and butyl acrylate, a copolymer of acrylic acid and ethylene , copolymer of ethylene and vinylcarbazole, block copolymer of ethylene and propylene, copolymer of ethylene, propylene and diene (SKEPT), polybutylene, polymethylpentene, polyisobutylene, copolymer of acrylonitrile and butadiene, polyisoprene, methyl copolymer and butylene, a copolymer of isoprene and isobutylene.

Methods for producing such polymers are described, in particular, in the following publications: Kunststoff-Handbuch Handbook, Volume IV, Munchen, Hanser Verlag; Ullmann, 4th edition, 19, p. 166 ff; Winnacker-Kuchler, 4th Edition, 6, p. 353-367; Elias and Vohwinkel, Neue Polymere Werkstoffe, Munchen, Hanser Verlag (1983); Franck and Biederbick, Kunststoff Kompendium, Wurzburg, Vogel Verlag (1984).

According to the invention, thermoplastic aromatic polycarbonates can also be used as thermoplastics, especially those based on the diphenols of formula I

wherein

A is a single bond, C ₁ -C ₅ alkylene, C ₂ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -S-, -SO ₂ -, -O-, -CO- or C ₆ -C ₁₂ arylene residue which may optionally be condensed with other heteroatom-containing aromatic rings,

residues B each independently of one another are C ₁ -C ₈ alkyl,

C ₆ -C ₁₀ aryl, particularly preferably phenyl, C ₇ -C ₁₂ aralkyl,

preferably benzyl, halogen, preferably chlorine, bromine,

x has independent values and denotes 0, 1 or 2, respectively, and

p is 1 or 0,

or alkyl substituted dihydroxyphenylcycloalkanes of formula II

wherein

R ¹ and R ^{2 are} independently hydrogen, halogen, preferably chlorine or bromine, C ₁ -C ₈ alkyl, C ₅ -C ₆ cycloalkyl, C ₆ -C ₁₀ aryl, preferably phenyl, and C ₇ -C ₁₂ aralkyl preferably phenyl-C ₁ -C ₄ alkyl, especially benzyl,

m is an integer from 4 to 7, preferably 4 or 5,

R ³ and R ⁴ , individually selected for each Z, are independently hydrogen or C ₁ -C ₆ alkyl, preferably hydrogen, methyl or ethyl, and

Z is carbon, provided that at least one atom ZR ³ and R ^{4 are} simultaneously alkyl.

Suitable for use for these purposes, diphenols of the formula I are, among others, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. Preferred as diphenols of formula I are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane.

Preferred diphenols of formula II include dihydroxydiphenyl-cycloalkanes with 5 and 6 ring C atoms in the cycloaliphatic residue (m = 4 or 5 in formula II), such as, for example, diphenols of formulas IIa, IIb and IIc

while 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexine (formula IIc) is particularly preferred.

Polycarbonates suitable according to the invention can be obtained in a known manner with a branched chain, namely, by incorporation of 0.05-2.0 mol%, calculated on the total amount of diphenols containing three or more three functional groups of compounds, for example, containing three or more phenolic groups, which, in particular, include

fluoroglucin,

4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) hepten-2,

4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane,

1,3,5-tri (4-hydroxyphenyl) benzene,

1,1,1-tri (4-hydroxyphenyl) ethane,

tri- (4-hydroxyphenyl) phenylmethane,

2,2-bis (4,4-bis (4-hydroxyphenyl) cyclohexyl) propane,

2,4-bis (4-hydroxyphenyl) isopropyl) phenol,

2,6-bis (2-hydroxy-5’-methylbenzyl) -4-methylphenol,

2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane,

hexa ether (4- (4-hydroxyphenylisopropyl) phenyl) orthoterephthalic acid,

tetra (4-hydroxyphenyl) methane,

tetra (4- (4-hydroxyphenylisopropyl) phenoxy) methane and

1,4-bis - ((4 ’-, 4’ ’- dihydroxytriphenyl) methyl) benzene.

Other trifunctional compounds include 2,4-dihydroxybenzoic acid, trimesinic acid, trimellitic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

Preferred polycarbonates along with bisphenol A homopolycarbonate include bisphenol A copolycarbonates with up to 15 mol%, calculated on mol. total amount of diphenols, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

The aromatic polycarbonates used can be partially replaced by aromatic polyester carbonates. Aromatic polycarbonates and / or aromatic polyester carbonates are known from the literature or can be obtained by methods known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964, and also DE- AS 1495626, DE-OS 2232877, DE-OS 2703376, DE-OS 2714544, DE-OS 3000610, DE-OS 3832396; for the preparation of aromatic polyester carbonates see, for example, DE-OS 3077934).

Aromatic polycarbonates and / or aromatic polyester carbonates can be prepared, for example, by reacting diphenols with carbonic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid halides, preferably with benzene dicarboxylic acid halides, according to a method where an interfacial reaction is used using chain terminating agents and, if necessary, using trifunctional or more than trifunctional chain splitters.

In addition, styrene copolymers of one or at least two ethylenically unsaturated monomers (vinyl monomers), such as, for example, styrene, α-methyl styrene, substituted styrene core, acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, can be used as thermoplastics. , N-substituted maleimides and esters of (meth) acrylic acid with 1-18 C-atoms in the alcohol component. These copolymers are resinous, thermoplastic and free of rubber. Styrene copolymers obtained by polymerization of at least one monomer from the group comprising styrene, α-methylstyrene and / or substituted at the core styrene, and at least one monomer from the group comprising acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride and / or N-substituted maleimide.

Particularly preferred weight ratios between styrene monomers and other vinyl monomers in a thermoplastic copolymer are 60-95 wt.% And 40-5 wt.%, Respectively.

The most preferred copolymers include copolymers of styrene with acrylonitrile and, if necessary, methyl methacrylate, α-methyl styrene and acrylonitrile and, if necessary, methyl methacrylate, or copolymers of styrene and α-methyl styrene with acrylonitrile and, if necessary, methyl methacrylate.

этих сополимеров (средневзвешенное значение, определяемое светорассеянием или седиментацией) составляет предпочтительно от 15000 до 200000 г/моль.Copolymers of styrene and acrylonitrile are known, and they can be obtained by radical polymerization, especially by emulsion, suspension polymerization, polymerization in solution or in bulk. Molecular mass

of these copolymers (weighted average determined by light scattering or sedimentation) is preferably from 15,000 to 200,000 g / mol.

Especially preferred copolymers are also statistical copolymers of styrene and maleic anhydride, which can be obtained from the corresponding monomers, preferably by continuous bulk polymerization or solution polymerization with incomplete monomer conversion. The proportion of both components in the statistical copolymers of styrene and maleic anhydride used according to the invention can vary within wide limits. The preferred content of maleic anhydride is from 5 to 25 wt.%.

Instead of styrene, the polymers may also contain core-substituted styrenes, such as p-methylstyrene, 2,4-dimethylstyrene and other substituted styrenes, for example α-methylstyrene.

) сополимеров стирола и ангидрида малеиновой кислоты может варьироваться в широких пределах. Предпочтителен диапазон от 60000 до 200000 г/моль. Предпочтительная характеристическая вязкость указанных продуктов составляет от 0,3 до 0,9 (определение в диметилформамиде при 25°С; см. Hoffmann, Kromer, Kuhn, Polymeranalytik I, Stuttgart (1977), стр.316 и далее).Molecular weight (number average molecular weight

) copolymers of styrene and maleic anhydride can vary within wide limits. A range of from 60,000 to 200,000 g / mol is preferred. The preferred intrinsic viscosity of these products is from 0.3 to 0.9 (determination in dimethylformamide at 25 ° C; see Hoffmann, Kromer, Kuhn, Polymeranalytik I, Stuttgart (1977), p. 316 onwards).

Grafted copolymers are also suitable as thermoplastics. This term in the context of the present description includes rubber-grafted elastic properties grafted copolymers that can be obtained mainly from at least two of the following monomers selected from the group consisting of chloroprene, butadiene-1,3, isopropene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and (meth) acrylic acid esters with 1-18 C-atoms in the alcohol component, i.e. copolymers described, for example, in Methoden der Organischen Chemie (Houben-Weyl), Volume 14/1, Georg Thieme-Verlag, Stuttgart (1961), pp. 393-406, and C.V. Bucknall "Toughened Plastics", Appl. Science Publishers, London (1977). Grafted copolymers that are partially crosslinked and contain a gel in an amount of more than 20 wt.%, Preferably more than 40 wt.% And especially more than 60 wt.% Are preferred.

Preferred grafted copolymers used include, but are not limited to, copolymers of styrene and / or acrylonitrile and / or alkyl esters of (meth) acrylic acid, grafted onto polybutadiene, copolymers of butadiene and styrene and acrylate rubbers; those. copolymers of the type described in DE-OS 1694173 (US Pat. No. 3,564,077); grafted with polybutadiene alkyl esters of acrylic or methacrylic acid, vinyl acetate, acrylonitrile, styrene and / or alkyl styrenes, copolymers of butadiene and styrene or butadiene and acrylonitrile, polyisobutenes or polyisoprenes, as described, for example, in DE-OS 3,919,377.

Particularly preferred polymers are, for example, ABS plastics, described in particular in DE-OS 2035390 (US Pat. No. 3,644,574) or DE-OS 2,248,242 (GB 1409275).

Grafted copolymers can be obtained by known methods, for example, bulk polymerization, suspension, emulsion polymerization, or by combined bulk polymerization and suspension polymerization.

As thermoplastic polyamides, polyamide 66 (polyhexamethylene adipinamide) or cyclic lactam polyamides with 6-12 C-atoms, preferably laurinlactam and particularly preferably ε-caprolactam, i.e. polyamide 6 (polycaprolactam), or copolyamides with the main components 6 and 66, or mixtures containing these polyamides as the main component. Polyamide 6 obtained by activated anionic polymerization or copolyamide obtained by activated anionic polymerization, the main component of which is polycaprolactam, is preferred.

Suitable ceramic materials are oxides, carbides and nitrides of the above metals, as well as composites based on these materials.

The topography of any surface can be described in principle on the basis of a composition composed of the Fourier components of the spatial frequencies f _x and f _y and the amplitudes a (f _x ) and a (f _y ) corresponding to these frequencies. Moreover, λ _x = f $\genfrac{}{}{0ex}{}{\text{-1}}{\text{x}}$ and λ _y = f $\genfrac{}{}{0ex}{}{\text{-1}}{\text{y}}$ denote the length of the structures at the x and y coordinates.

A technique is widely used in the technique for determining the so-called power spectral density S ₂ (f _x , f _y ). The average spectral power density is proportional to the average square of all amplitudes at the corresponding spatial frequencies f _x and f _y . If we are talking about an isotropic surface, then the topography of such a surface can be characterized using the power spectral density PSD (f) averaged over the polar angle. The power spectral density PSD (f), although it is a two-dimensional function of dimension [length] ⁴ , nevertheless, both directions of reference coincide, and therefore only one of them is considered. The corresponding methodology for such a calculation is described, for example, in a publication by C. Ruppe and A. Duparre, Thin Solid Films, 288 (1996), p. 9, equation (2).

Depending on the measurement method used to determine the topography, the value of the power spectral density is either obtained directly, or the results obtained must be converted into the power spectral density PSD (f) by the Fourier transform of the data on the height of the irregularities of the profile determining the surface topography. The methodology for such a calculation is described in the above publication by C. Ruppe and A. Duparre, Thin Solid Films, 288 (1996), p. 9, which is incorporated herein by reference.

The ultra-phobic surface profile is characterized by the presence of elevations (protrusions) and depressions (depressions) under a drop of liquid, the height, respectively, of which depth varies from 0.1 nm to 1 mm. Due to such a wide range of values, it is currently impossible to determine the surface topography using a single measurement method, and therefore, to accurately determine the surface topography, one has to use a combination of three methods of measuring and processing the results. These measurement methods are:

1) white light interference interferometry (IHD),

2) scanning atomic force microscopy (CASM),

3) scanning tunneling microscopy (STM).

These measurement methods make it possible to determine the power spectral density PSD (f) in each case locally in relatively narrow spatial frequency ranges Δf. Then these values of the locally determined power spectral density are combined into the final (total) power spectral density PSD (f) in the spatial frequency range from f = 10 ⁻³ μm ⁻¹ to f = 10 ³ μm ⁻¹ . A method for combining locally obtained PSD curves is described, for example, by C. Ruppe and A. Duparre in Thin Solid Films, 288 (1996), p. 10, which publication is incorporated herein by reference.

White light interference interferometry (IHD) is used to determine the power spectral density in the range of spatial frequencies Δf from 1 × 10 ^-3 μm ^-1 to 1 μm ^-1 , while

for a portion of the measured surface with a size of 1120 × 1120 μm, measurements are carried out in the spatial frequency range Δf from 9 × 10 ^-4 μm ^-1 to 2 × 10 ^-1 μm ^-1 ,

for a portion of the measured surface with a size of 280 × 280 μm - in the range of spatial frequencies Δf from 4 × 10 ^-3 μm ^-1 to 9 × 10 ^-1 μm ^-1 ,

for a portion of the measured surface with a size of 140 × 140 μm - in the range of spatial frequencies Δf from 7 × 10 ^-3 μm ^-1 to 2 × 10 ⁰ μm ^-1 .

When measuring by this method, the height of the irregularities of the profile z (x, y) is determined using the interferometer used to measure interference in white light, while z denotes the height above some arbitrarily chosen base level z ₀ at the corresponding point x or y. The conditions for such studies and the measurement procedure are described in more detail by RJ Recknagel and G. Notni at Optics Commun. 148, pp. 122-128 (1998). Recalculation of data on the height of profile irregularities is carried out similarly to how this is carried out with the scanning atomic force microscopy considered below, and scanning tunneling microscopy, respectively.

Scanning atomic force microscopy (CASM) is used to determine the power spectral density in the spatial frequency range Δf from 1 × 10 ^-2 μm ^-1 to 1 × 10 ² μm ^-1 , and when measured by this method, which is widely known to specialists, the height of the irregularities profile z _{m, n of the} surface is recorded using a scanning atomic force microscope in contact or vibration mode. During measurements using this method, various sections (sampling ranges) of size L × L are scanned. Based on these scanned sections and the number of N points, it is possible to calculate the minimum, respectively, maximum spatial frequency that can be investigated in each scanned section, the following condition being true: f _max = N / 2L, respectively f _min = 1 / L. It is preferable to use 512 measurement points in each scanned area, and thus, in the scanned area of 50 × 50 μm in size, measurements are carried out in the spatial frequency range Δf from 2 × 10 ^-2 μm ^-1 to 5 μm ^-1 ,

on the scanned area of 10 × 10 μm in the spatial frequency range Δf from 1 × 10 ^-1 μm ^-1 to 3 × 10 ¹ μm ^-1 and

on the scanned area of 1 × 1 μm in size - in the range of spatial frequencies Δf from 1 μm ^-1 to 3 × 10 ² μm ^-1 .

The height of the profile irregularities z _{m, n} is determined relative to some arbitrarily selected base level z ₀ , where m and n are the coordinates of the measurement points in the x direction, respectively y, which are spaced from each other with an equal step ΔL. Data on the height of the profile irregularities are converted to the average power spectral density of the PSD using equations 1 and 2 presented for this purpose by S. Ruppe and A. Duparre, Thin Solid Films, 288 (1996), p. 9.

Scanning tunneling microscopy (STM) is used to determine the power spectral density in the spatial frequency range Δf from 1 × 10 ¹ μm ^-1 to 1 × 10 ³ μm ^-1 , and when measured by this method, which is widely known to specialists, the height of the profile irregularities z _{m , n} surfaces are recorded using a scanning (raster) tunnel microscope. When measured by this method, various sections of size L × L are also scanned. Based on these scanned sections and the number of N points, it is possible to calculate the minimum, respectively, maximum spatial frequency that can be investigated in each scanned section, the following condition being true: f _max = N / 2L, respectively f _min = 1 / L. It is preferable to use 512 measurement points in each scanned area, and thus, in the scanned area of 0.5 × 0.5 μm, the measurements are carried out in the spatial frequency range Δf from 2 μm ^-1 to 5 × 10 ² μm ^-1 ,

on the scanned area of 0.2 × 0.2 μm in the spatial frequency range Δf from 5 μm ^-1 to 1 × 10 ³ μm ^-1 ,

on the scanned area of 0.1 × 0.1 μm in size - in the range of spatial frequencies Δf from 1 × 10 ¹ μm ^-1 to 3 × 10 ³ μm ^-1 .

The height of the profile irregularities z _{m, n} is determined with respect to some arbitrarily chosen base level z ₀ , where m and n are the coordinates of the measurement points in the x, y direction, which are spaced from each other with an equal step ΔL. Data on the height of the profile irregularities are converted to the average power spectral density of the PSD using equations 1 and 2 presented for this purpose by S. Ruppe and A. Duparre, Thin Solid Films, 288 (1996), p. 9.

In more detail, the conditions for conducting such studies and the methodology for measuring CASM and STM are described, for example, in S.N. Magonov and M.N. Whangbo, Surface Analysis with STM and AFM, VCH, Weinheim (1966), in particular, pp. 47-62.

Obtained by various measurement methods, respectively, for different scanned sections, the PSD curves are combined into a PSD (f) curve in the spatial frequency range from 10 ⁻³ μm ⁻¹ to 10 ³ μm ⁻¹ . The PSD (f) curve is constructed from the data obtained in accordance with the method described by C. Ruppe and A. Duparre in Thin Solid Films, 288 (1996), pp. 10-11. Figure 1-4 in this publication shows the PSD (f) curves obtained as a result of such a combination as a double logarithmic dependence in which log (PSD (f) / nm ⁴ ) is a function of log (f / μm ^-1 ).

The technique for determining the spectral power density of this type of energy has been known for a long time and is used to obtain characteristics of other surfaces as well as for other, very different purposes (cf., for example, JC Stover, Optical Scattering, 2nd ed. (1995), SPIE Press, Bellingham, Washington, USA, chapter 2, p. 29 ff., and chapter 4, p. 85 ff.).

To more clearly confirm the features of the topography of surfaces determined in accordance with the invention, based on the power spectral density PSD (f), the spatial frequency-dependent amplitude a (f) of the sinusoidal Fourier components is calculated. For this purpose, formulas (4.19) are used on p. 103, as well as table 2.1 on p. 34 and table 2.2 on p. 37 of the above publication by J.C. Stover, Optical Scattering, 2nd ed. (1995), SPIE Press, Bellingham, Washington, USA.

The amplitudes a (f) of the sinusoidal Fourier components normalized to the corresponding lengths of the structures λ = f ⁻¹ are shown in FIGS. 5-8 as a function of S

the logarithm of the spatial frequency log (f / μm ^-1 ).

When creating the invention, it was unexpectedly found that a surface having a structure at which the integral of the function S (logf) = a (f) · f, calculated between the lower limit of integration f ₁ / μm ^-1 = -3 and the upper limit of integration f ₂ / μm ^-1 , exceeds 0.5, and made of a hydrophobic material or coated with a hydrophobic material, has ultra-phobic properties, so that the contact angle of a water drop on such a surface exceeds 150 °.

This new, completely unexpected effect allows you to largely accurately determine in advance the possible subsequent technological operations in the manufacture of ultra-phobic surfaces. The main idea in this case is as follows: in Figs. 5-8, the logarithmic frequency scale log (f) shows the structure amplitudes a (f) · f normalized to the corresponding wavelengths λ = f ¹ for different frequencies f. The value a (f) · f = 0.5 means, for example, that the normalized amplitude, i.e. the “roughness” defined for this Fourier component is half its wavelength λ = f ¹ . Thus, the integral of equation (1) reflects the following:

- the average value of all normalized amplitudes a (f) · f at separate different frequencies must exceed a value of 0.5, in other words, to obtain an ultra-phobic surface, the roughness averaged over all frequencies must be maximum;

- various spatial frequencies with equal weights are included in this sum (expressed in terms of log (f)).

Thus, it does not matter in the frequency range of which individual roughnesses are located.

Based on this, the specialist will be able to easily establish that roughening the surface, for example, through the use of spherical (spherical) particles of the same size will not give the desired effect. This effect, however, can be achieved if the surface of the particles is additionally roughened due to smaller structures using, for example, small particles that are deposited on large particles or adhered to them, but in any case and other particles should not be separated from each other.

Further, it is obvious that, for example, when roughening a surface by applying scratches to it (scratching), (for example, using abrasive particles), one should take into account the fact that the recesses (depressions) formed in this way should, in turn, be as rough as possible in a range that does not go beyond the next order of magnitude. If this condition is not observed, additional operation will be required to roughen these primary depressions.

It should be noted at the same time that the new approach described above does not imply any restrictions regarding the shape or profile of the recesses, respectively, of the roughness structures. So, in the example where particles are applied on the surface to roughen up and form the structure required to obtain an ultrafobic surface, the microsubstructures of the particles themselves can have a completely different shape (i.e., a different spectrum of spatial frequencies) compared to the structure that these particles themselves particles form on the surface.

Thanks to the approach described above, when determining the frequency-dependent amplitudes of the Fourier components using the power spectral density, it opens, among other things, a new, not yet known opportunity to test various materials with very different surface structures for their ultrafobic properties and to characterize them accordingly.

The object of the present invention is further a method for testing surfaces for their ultrafobic properties, which is characterized in that a thin layer, primarily from 10 to 100 nm thick, of a noble metal, primarily gold, or GaAs as an adhesion promoter is applied by spraying, then cover with a layer of auxiliary phobic substance, preferably decantiol, and then analyze the surface topography, primarily using scanning tunneling microscopy, atomic force microscopy and interferometer of white light interference in their combination, and based on the data obtained, the spatial frequencies f of the individual Fourier components and their amplitudes a (f), expressed through the integral of the function S

calculated between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration log (f ₂ / μm ^-1 ) = 3, and if necessary, measure the contact angle formed by water located on the surface treated in this way .

Due to the applied adhesion promoter layer (usually gold, with a thickness of 10 to 100 nm) and the choice of a homogeneous phobic agent, it is possible to study a variety of materials, the surface of which is suitable for imparting ultrafobic properties, regardless of the materials used. In this way, it is possible to compare different surface structures with each other.

An ultra-phobic surface is preferred, characterized in that a layer of a hydrophobic phobic auxiliary agent, especially an anionic, cationic, amphoteric or non-ionic surfactant, is deposited on it.

Surfactants of any molar mass are acceptable as an auxiliary phobic agent. These compounds are preferably cationic, anionic, amphoteric, or nonionic surfactants, as described, for example, in the Surfactants Europa, A Dictionary of Surface Active Agents available in Europe, ed. Gordon L. Hollis, Royal Society of Chemistry, Cambridge (1995).

Examples of anionic auxiliary phobic agents include alkyl sulfates, esterified sulfates, esterified carboxylates, phosphoric acid esters, sulfosuccinates, sulfosuccinamides, paraffinsulfonates, olefinsulfonates, sarcosinates, isothionates, taurates and ligno compounds.

As cationic auxiliary phobic agents, mention may be made, for example, of quaternary alkyl ammonium compounds and imidazoles.

As amphoteric auxiliary phobic agents, betaines, glycinates, propionates and imidazoles are acceptable, among others.

Among the nonionic auxiliary phobic agents, mention may be made, for example, of alkoxylates, alkylamides, esters, amine oxides, alkyl polyglycosides, alkyl sulfides and alkyl disulfides. In addition to the above, reaction products of alkylene oxides with alkylated compounds, such as, for example, fatty alcohols, fatty amines, fatty acids, phenols, alkyl phenols, aralkyl phenols, such as styrene and phenol condensates, carboxylic amides and resin acids, can be used.

Particularly preferred auxiliary phobic agents in which from 1 to 100%, most preferably from 60 to 95% of the hydrogen atoms are replaced by fluorine atoms. Examples include perfluorinated alkyl sulfate, perfluorinated alkyl sulfonates, perfluorinated alkyl sulfides, perfluorinated alkyl disulfides, perfluorinated alkyl phosphonates, perfluorinated alkyl phosphinates and perfluorinated carboxylic acids.

It is preferable to use compounds with a molar mass of M _W in the range of from more than 500 to 1,000,000, preferably from 1,000 to 500,000, and particularly preferably from 1,500 to 20,000 as polymeric auxiliary phobic agents for applying a hydrophobic coating to the surface, and particularly preferably from 1,500 to 20,000. Such polymer auxiliary phobic agents may be nonionic, anionic, cationic or amphoteric compounds. In addition to the homo- and copolymers, grafted polymers and grafted copolymers, as well as random block copolymers, mentioned as polymeric auxiliary phobic agents. The most preferred polymeric auxiliary fobbing agents include block copolymers of types AB, BAB and ABC. In block copolymers of type AB or BAB, the A unit is a hydrophilic homopolymer or copolymer, and the B block is a hydrophobic homopolymer or copolymer or a salt thereof.

Particularly preferred are also anionic polymeric auxiliary phobic agents, especially condensation products of aromatic sulfonic acids with formaldehyde and alkylnaphthalene sulfonic acids or obtained from formaldehyde, naphthalene sulfonic acids and / or benzenesulfonic acids, condensation products from optionally substituted phenol with formaldehyde and sodium bisulfite.

Further preferred are condensation products obtained by reacting naphthols with alkanols, alkylene oxide addition products, and at least partially converting the terminal hydroxy groups to sulfo groups or half esters of maleic acid and phthalic acid or succinic acid.

According to another preferred embodiment, as an auxiliary phobic agent, one is selected from the group consisting of sulfonic succinic acid esters and also alkylbenzenesulfonates. Sulfated, alkoxylated fatty acids or their salts are also preferred. Under alkoxylated alcohols from fatty acids are meant primarily saturated or unsaturated alcohols from C ₆ -C ₂₂ fatty acids containing 5-120, preferably 6-60 and most preferably 7-30 ethylene oxide units, in particular stearyl alcohol. Sulfated alkoxylated alcohols from fatty acids are preferably in the form of salts, especially alkali metal salts or amine salts, preferably in the form of a diethylamine salt.

Another object of the invention is a method for producing an ultrafobic surface, which is characterized in that the mold is made in the form of a negative, i.e. a form with a reverse imprint from the corresponding topographic surface required by the ultraphobic surface, made of a mixture of plastic and a hydrophobic or especially oleophobic additive, which during curing is deposited in the form of a thin film between the surface of the mold and the molded plastic product.

According to another preferred embodiment, said mold is molded from a polymeric material, and then a hydrophobic or especially oleophobic coating is applied to this molded article from the polymeric material.

As used in the context of the present description, the term "form" means any form that can be made by pouring from polymeric materials or from mixtures of such materials. Moreover, the surface of the form is made in such a way that its topography is a reverse imprint, or, in other words, the negative of any desired ultrafobic surface.

It is preferable, however, that the topography of the ultrafobic surface corresponds to an etched, anodized and hot water and steam treated aluminum surface, which is obtained by the methods described in German application 1986 198638.7, and it is envisaged that these surfaces should not have any hydrophobic coating. The surface of the aluminum base is subjected to electrochemical etching in an acidic environment, anodic oxidation and hot water or steam at a temperature in the range from 50 to 100 ° C and, if necessary, coated with a layer of adhesion promoter.

Depending on the material used, the surface can be formed by pouring or spraying a molten or dissolved thermoplastic, respectively, not yet cured thermoplastic. Appropriate technology is well known to a person skilled in the art.

Another object of the present invention is a method for producing a surface with ultrafobic properties, which is characterized in that the surface obtained from the inverse (negative), the profile of which corresponds to the desired ultrafobic surface, is formed using a mixture of plastic and a hydrophobic, or especially oleophobic additive, which during curing, it is deposited in the form of a thin film between the surface of the mold and the molded plastic product.

According to another preferred embodiment, said mold is molded from a polymeric material, and then a hydrophobic or especially oleophobic coating is applied to this molded article from the polymeric material.

Under used in the context of the present description of the form refers to any form that can be made by pouring from polymeric materials or from mixtures of such materials. Moreover, the surface of the mold is made in such a way that its topography is the inverse of any surface that can be used subsequently for structuring (profiling) of the desired ultra-phobic surface.

It is preferable, however, that the topography of the ultraphobic surface corresponds to an etched, anodized and hot water and steam treated aluminum surface, which is obtained by the methods described in German application 1986 198638.7, and it is envisaged that these surfaces should not have any hydrophobic coating. The surface of the aluminum base is subjected to electrochemical etching in an acidic environment, anodic oxidation and hot water or water vapor at a temperature in the range from 50 to 100 ° C and, if necessary, coated with a layer of adhesion promoter.

Depending on the material used, the surface can be formed by pouring or spraying a molten or dissolved thermoplastic, respectively, not yet cured thermoplastic. Appropriate technology is well known to a person skilled in the art.

The method of the invention is based, as it was unexpectedly found, on the fact that a surface whose topography serves as a “prototype” of the desired ultrafobic surface can be formed directly, and the resulting negative can be reused to form subsequent ultrafobic surfaces. Thanks to this approach, there is no need for expensive production each time a new negative with the topography of the required ultrafobic surface, as provided in the prior art.

Using the method according to the invention, it is possible to obtain ultrafobic surfaces, characterized in that the contact angle of the liquid droplet located on the surface is ≥155 °. The object of the invention in accordance with this are also ultra-phobic surfaces obtained by the proposed method.

When carrying out both variants of the proposed molding method, plastics from the group of duroplastics or thermoplastics can be used. It is advisable to choose Duroplast primarily from the group including diallyl phthalate resin, epoxy resin, urea-formaldehyde resin, melamine-formaldehyde resin, melamine-phenol-formaldehyde resin, phenol-formaldehyde resin, polyimide, silicone rubber and unsaturated resin. It is advisable to choose a thermoplastic primarily from the group comprising a thermoplastic polyolefin, for example polypropylene or polyethylene, polycarbonate, polyester carbonate, polyesters, for example PBT or PET, polystyrene, styrene copolymer, styrene-acrylonitrile copolymer, rubber grafted acrylic copolymer, styrene copolymer copolymer, styrene (ABS plastic), polyamide, polyurethane, polyphenylene sulfide, polyvinyl chloride or any possible mixture of these polymers.

According to the invention, the above form is made by pouring a mixture consisting of a polymer, such as PC (polycarbonate) or PMMA (polymethylmethacrylate), and a hydrophobic and / or oleophobic additive, which during curing is deposited in the form of a thin film between the negative surface and the manufactured molded product.

Surfactants with any molar mass are acceptable as an additive. These compounds are preferably cationic, anionic, amphoteric, or nonionic surfactants, as described, for example, in the Surfactants Europa, A Dictionary of Surface Active Agents available in Europe, ed. Gordon L. Hollis, Royal Society of Chemistry, Cambridge (1995).

As anionic additives, for example, alkyl sulfates, esterified sulfates, esterified carboxylates, phosphoric esters, sulfosuccinates, sulfosuccinamides, paraffinsulfonates, olefinsulfonates, sarcosinates, isothionates, taurates and ligno compounds can be mentioned.

As cationic additives, for example, quaternary alkyl ammonium compounds and imidazoles can be mentioned.

As amphoteric additives, betaines, glycinates, propionates and imidazoles are acceptable, among others.

Among nonionic additives, for example, alkoxylates, alkylamides, esters, amine oxides, alkyl polyglycosides, alkyl sulfides and alkyl disulfides can be mentioned. In addition to the above, reaction products of alkylene oxides with alkylated compounds, such as, for example, fatty alcohols, fatty amines, fatty acids, phenols, alkyl phenols, aralkyl phenols, such as styrene and phenol condensates, carboxylic amides and resin acids, can be used.

Particularly preferred additives in which from 1 to 100%, most preferably from 60 to 95% of the hydrogen atoms are replaced by fluorine atoms. Examples include perfluorinated alkyl sulfate, perfluorinated alkyl sulfonates, perfluorinated alkyl sulfides, perfluorinated alkyl disulfides, perfluorinated alkyl phosphonates, perfluorinated alkyl phosphinates and perfluorinated carboxylic acids.

As polymeric additives for applying a hydrophobic coating or as a polymeric hydrophobic material for a surface, it is preferable to use compounds with a molar mass M _W in the range of from more than 500 to 1,000,000, preferably from 1,000 to 500,000, and particularly preferably from 1,500 to 20,000. Such polymer additives can be nonionic, anionic, cationic or amphoteric compounds. In addition to those named as polymer additives, homo- and copolymers, grafted polymers and grafted copolymers, as well as random block copolymers, can be used. The most preferred polymer additives include block copolymers of type AB, BAB and ABC. In block copolymers of type AB or BAB, the A unit is a hydrophilic homopolymer or copolymer, and the B block is a hydrophobic homopolymer or copolymer or a salt thereof.

Particularly preferred are also anionic polymer additives, especially condensation products of aromatic sulfonic acids with formaldehyde and alkylnaphthalene sulfonic acids or obtained from formaldehyde, naphthalene sulfonic acids and / or benzenesulfonic acids, condensation products from optionally substituted phenol with formaldehyde and sodium bisulfite.

Further preferred are condensation products obtained by reacting naphthols with alkanols, alkylene oxide addition products, and at least partially converting the terminal hydroxy groups to sulfo groups or half esters of maleic acid and phthalic acid or succinic acid.

According to another preferred embodiment, as an additive, one is selected from the group consisting of sulfonic succinic acid esters and also alkylbenzenesulfonates. Sulfated, alkoxylated fatty acids or their salts are also preferred. Under alkoxylated alcohols from fatty acids are meant primarily saturated or unsaturated alcohols from C ₆ -C ₂₂ fatty acids containing 5-120, preferably 6-60 and most preferably 7-30 ethylene oxide units, in particular stearyl alcohol. Sulfated alkoxylated alcohols from fatty acids are preferably in the form of salts, especially alkali metal salts or amine salts, preferably in the form of a diethylamine salt.

Thanks to this technology, the hydrophobic or oleophobic coating is no longer required to be applied to the molded product, as a result of which there is no need to carry out the corresponding technological operation envisaged in other cases.

One of the advantages of the ultra-phobic surfaces according to the invention is their ability to self-clean, such self-cleaning can occur during rain or when washing with any stream of water. Since the surface has ultra-phobic properties, water droplets located on the surface slide off it, entraining dirt particles along with it, which have only extremely weak adhesion to the surface and are thus removed from the surface. Such self-cleaning takes place not only under the influence of water, but also oil.

The object of the invention is also a structural material or building material having an ultra-phobic surface according to the invention.

The ultra-phobic surface of the invention can find application in a wide variety of technical fields. The object of the invention in accordance with this is the use of the proposed ultra-phobic surfaces for the following purposes:

An ultra-phobic surface can be provided for ship hulls in order to reduce friction resistance.

Another possibility of using ultra-phobic surfaces is due to the need to treat the corresponding working surface to prevent adhesion of water to it in order to avoid icing. An example is the surface of heat exchangers used in refrigeration units, or the fuselages of aircraft.

In addition, the surfaces of the invention are suitable for application to building facades, roofs, monuments, and the like. in order to give them the ability to cleanse themselves.

Another object of the invention is the use of the proposed ultra-phobic surfaces to reduce the frictional force of the lining of vehicle bodies, aircraft fuselages or ship hulls.

Another object of the invention is the use of ultra-phobic surfaces as self-cleaning coatings or cladding of buildings, roofs, windows, ceramic building materials, used, for example, for plumbing equipment, household appliances, etc.

The object of the invention is further the use of ultra-phobic surfaces as an anti-corrosion coating of metal products. The object of the invention is the use of the proposed ultra-phobic surfaces as transparent panels in the case of applying them to a transparent substrate or as a coating layer applied to transparent glasses, especially quartz or polymer glasses, intended, in particular, for solar panels, motor vehicles or greenhouses .

Another object of the invention is the use of ultra-phobic surfaces as a coating for containers intended for the respective liquids, which, for example, need to be dosed or fed into these containers in a certain way. This includes, in particular, cannulas, sleeves (hoses) or storage containers.

Another object of the invention is a method for producing a surface with ultrafobic properties based on the A1Mg ₃ alloy, which is characterized in that this surface is cleaned, etched, subjected to anodic oxidation, passivated in boiling water, and if necessary, a layer of noble is applied onto it, primarily by spraying. metal as an adhesion promoter, primarily from gold, with a thickness of 10 to 100 nm and finally coated with a hydrophobic material, primarily anionic, cationic, amphoteric or nonionic surface-active nym compound fobiruyuschego as an auxiliary agent.

Instead of the integral of the function S

calculated between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration log (f ₂ / μm ^-1 ) = 3 and exceeding 0.5, the integral of function F can also be used to determine the ultra-phobic surface

calculated between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration log (f ₂ / μm ^-1 ) = 3. In order to classify a surface as a category of surfaces with ultrafobic properties, the integral of the indicated function F in the range of its positive values must exceed 5. It was already proposed to use a similar function F to describe the surface topography in DE 19860136.0. However, the advantage associated with the description of surface topography using equation (1), i.e. using the function S, is that the value of the integral of this function S (logf) is more indicative. This is due to the fact that the indicated value is proportional to the normalized amplitude of all Fourier components <a (f) · f>, averaged on a logarithmic frequency scale in the interval -3≤log (f / μm ^-1 ) ≤3. Thus, the criterion found, which the obtained ultraphobic surfaces must satisfy, can be summarized as follows: the normalized average of all Fourier amplitudes <a (f) · f> defined on the logarithmic frequency scale should be greater than 0.5 / 6 = 0.08. Thus, the Fourier amplitude for the “average” frequency should be at least about 8% of the length of the structure.

To compare the results obtained using both equations (1) and (2), you can refer to the following examples 1-6 and the attached figures 10 and 11, which additionally used the function F, discussed in the application DE 19860136.0.

Below the invention is explained in more detail by examples with reference to the accompanying drawings, which show:

figure 1 - curves PSD (f) obtained for proposed in the invention ultrafobic surfaces from examples 1-6,

figure 2 - curves PSD (f) obtained for proposed in the invention ultra-phobic surfaces of examples 7-9,

figure 3 - curves PSD (f) obtained for proposed in the invention ultra-phobic surfaces from examples 10-11,

figure 4 - curves PSD (f) obtained for proposed in the invention ultrafobic surfaces from examples 12-13,

figure 5 - graphs of frequency-dependent amplitudes a (f) of the Fourier components for proposed in the invention surfaces from examples 1-6,

figure 6 - graphs of frequency-dependent amplitudes a (f) of the Fourier components for the proposed in the invention surfaces from examples 7-9,

figure 7 - graphs of frequency-dependent amplitudes a (f) of the Fourier components for the proposed in the invention surfaces from examples 10-11,

on Fig - graphs of frequency-dependent amplitudes a (f) of the Fourier components for proposed in the invention surfaces from examples 12-13,

figure 9 - dependence of the contact angle of the water drop on the integral of the function S (logf) = a (f) · f calculated between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration log (f ₂ / μm ^-1 ) = 3, for various surfaces from examples 1-13,

figure 10 is a graph of frequency-dependent amplitudes a (f) of the Fourier components of the surfaces of the invention of examples 1-6 in the form of a function F (logf), presented in the form of a double logarithmic dependence (in accordance with application DE 19860136.0),

figure 11 - dependence of the contact angle of the water drop on the integral of the function F (logf), calculated in the range of positive values of the function F between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration log (f ₂ / μm ^-1 ) = 3, for various surfaces from examples 1-6 (in accordance with the application DE 19860136.0).

Examples

General explanation of examples

1. Determination of surface topography

To determine the surface topography, the latter was examined using a scanning tunneling microscope, a scanning atomic force microscope, white light interference interferometry, and angular resolution light scattering.

For scanning tunneling microscopy, a Nanoscope III microscope from Digital Instruments, Santa Barbara, pc. California, which worked in direct current mode. The measurements were carried out in air at room temperature with a mechanically retractable platinum-iridium tip. In this case, sections of areas L ² 500 × 500 nm ² , 200 × 200 nm ² and 50 × 50 nm ^{2 were} sequentially scanned with the number of points in each section N ² = 512 × 512 with a step between these points ΔL = N / L.

The data on the height of the profile irregularities were converted into the average power spectral density of the PSD according to equations (1) and (2) from the publication of C. Ruppe and A. Duparre, Thin Solid Films, 288 (1996), p. 9.

Scanning atomic force microscopy measurements were performed using a DIMENSION 3000 type atomic force microscope (Digital Instruments, Santa Barbara, USA) in a continuous mode. The measurements were carried out in air at room temperature. In this case, a silicon tip with a radius of about 10 nm was used and sections of areas L ² 1 × 1 μm ² , 10 × 10 μm ² and 50 × 50 μm ^{2 were} sequentially scanned with the number of points in each section N ² = 512 × 512 with a step between these points ΔL = N / L.

For white light interference interferometry, a LEICA DMR microscope from Leica, Wetzlar, was used. In this case, we studied areas with an area of 140 × 140 μm ² , 280 × 280 μm ² , 1120 × 1120 μm ² and 2800 × 2800 μm ² with the number of points in each section 512 × 512.

The PSD (Δf) curves obtained using the above measurement methods were then combined into a single PSD (f) curve, which was constructed as a double logarithmic dependence according to Figs. 1-4, with the PSD power spectral density being divided by nm ⁴ , and the spatial frequency f dividing by μm ^{-1 was} converted into dimensionless quantities.

Calculation of frequency-dependent amplitudes a (f)

Frequency-dependent amplitudes a (f) were determined based on PSD (f) curves using the following formula

.

.

As a constant D, which determines the limits of integration, in which the function PSD (f) is considered as a constant, in all cases under consideration, a value of D equal to 1.5 was used.

This formula basically corresponds to the calculation of spatial frequency-dependent amplitudes, also described by J.C. Stover in Optical Scattering, 2nd Edition, SPIE Press, Bellingham, Washington, USA (1995) (see formula (4.19) on page 103, as well as table 2.1 on page 34 and table 2.2 on page 37).

Example 1

An A1Mg ₃ plate polished with finishing rolls with an area of 35 × 35 mm ² and a thickness of 0.5 mm was degreased first with distilled chloroform and then for 20 s in aqueous NaOH (5 g / l) at 50 ° С. After that, it was treated with etching in H ₃ PO ₄ (100 g / l) for 20 s, washed in distilled water for 30 s, and electrochemical etching was carried out for 90 s in a mixture of HCl / H ₃ BO ₃ (respectively 4 g / l ) at 35 ° С at a current density of 120 mA / cm ^{2 of an} alternating voltage of 35 V. After a 30-second washing in distilled water and a 30-second washing with alkali in aqueous NaOH (5 g / l), they were repeatedly washed for 30 s in distilled water and then anodic oxidation in H ₂ SO ₄ (200 g / l) was carried out for 90 s at 25 ° C at a current density of 30 mA / cm ² constant voltage 50 V. After that, it was washed in distilled water for 30 s, in NaHCO ₃ (20 g / l) for 60 s at 40 ° C, and then again for 30 s in distilled water and finally for 1 h dried in an oven at 80 ° C.

A layer of gold approximately 50 nm thick was sprayed onto the plate processed in this way, after which the sample was coated for 24 hours in a state of immersion in a solution of n-decantiol in ethanol (1 g / l) at room temperature in a closed vessel and completion washed with ethanol and dried.

The static contact angle of the water droplet located on such a surface is 167 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl rolls off it.

The topography of this surface was described and investigated in the same way as described above in section "1. Determination of surface topography", and the obtained measurement data are presented in the form of curve 1 in figure 1.

The integral of the normalized Fourier amplitudes S (log f), calculated in the interval between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration

log (f ₂ / μm ^-l ) = 3 is 0.81.

Example 2

In this example, the processing of the A1Mg ₃ plate and coating on it was carried out analogously to Example 1, however, with the difference that, in addition, before the deposition of the gold layer, etching in 1 M NaOH was performed for 20 s, then it was washed in distilled for 30 s water, and then in ethanol and for 1 h, dried in an oven at 80 ° C.

The static contact angle of the water droplet located on such a surface is 161 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl rolls off it.

The topography of this surface was described and investigated in the same way as described above in section "1. Determination of surface topography", and the obtained measurement data are presented in the form of curve 2 in figure 1.

The integral of the normalized Fourier amplitudes S (log f), calculated in the interval between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration

log (f ₂ / μm ^-1 ) = 3 is 0.58.

Reference Example 3

In this example, the processing of the A1Mg ₃ plate and coating on it was carried out analogously to Example 2, with the difference, however, that the etching was carried out for 120 s in 1 M NaOH.

The static contact angle of the water droplet located on such a surface is 150 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl does not roll off it.

The topography of this surface was described and investigated in the same way as described above in section "1. Determination of surface topography", and the obtained measurement data are presented in the form of curve 3 in figure 1.

The integral of the normalized Fourier amplitudes S (log f), calculated in the interval between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration

log (f ₂ / μm ^-1 ) = 3 is 0.46.

Reference Example 4

In this example, a polycarbonate substrate with an area of 35 × 35 mm ² and a thickness of 1 mm was applied for subsequent spraying onto it a layer of aluminum with a thickness of 200 nm. After that, the sample was treated in distilled water at 100 ° С for 30 min, then washed in distilled water at room temperature for 30 s and dried in an oven at 80 ° С for 1 h.

Next, a layer of gold approximately 50 nm thick was sprayed onto the sample treated in this way. Then, this sample was exposed for 24 h in a state of immersion in a solution of n-decantiol in ethanol (1 g / l) at room temperature in a closed vessel, and the coating was washed and finally washed with ethanol and dried.

The static contact angle of the water droplet located on such a surface is 135 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl does not roll off it.

The topography of this surface was described and investigated in the same way as described above in section "1. Determination of surface topography", and the obtained measurement data are presented in the form of curve 4 in figure 1.

The integral of the normalized Fourier amplitudes S (log f), calculated in the interval between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration

log (f ₂ / μm ^-1 ) = 3 is 0.28.

Reference Example 5

In this example, an A1Mg ₃ plate polished with finishing rolls with an area of 35 × 35 mm ² and a thickness of 0.5 mm was degreased with distilled chloroform. After a 30 second wash in distilled water for 600 s, anodic oxidation was performed in H ₂ SO ₄ (200 g / l) at 20 ° C at a current density of 10 mA / cm ^{2 of a} constant voltage of 35 V. Then it was washed in distilled water and in for 1 h, dried at 80 ° C in an oven.

Next, a layer of gold approximately 50 nm thick was sprayed onto the sample treated in this way. Then, this sample was exposed for 24 h in a state of immersion in a solution of n-decantiol in ethanol (1 g / l) at room temperature in a closed vessel, and the coating was washed and finally washed with ethanol and dried.

The static contact angle of the water droplet located on such a surface is 122 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl does not roll off it.

The topography of this surface was described and investigated in the same way as described above in section "1. Determination of surface topography", and the obtained measurement data are presented in the form of curve 5 in figure 1.

The integral of the normalized Fourier amplitudes S (log f), calculated in the interval between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration

log (f ₂ / μm ^-1 ) = 3 is 0.14.

Reference Example 6

In this example, a 200 nm thick gold layer was sprayed onto an untreated polishing single-crystal silicon wafer and a 24-hour gold sample was applied to this sample immersed in a solution of n-decantiol in ethanol (1 g / l) at room temperature in a closed vessel. coating, then washed with ethanol and dried.

The static contact angle of the water droplet located on such a surface is 115 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl does not roll off it.

The topography of this surface was described and investigated in the same way as described above in section "1. Determination of surface topography", and the obtained measurement data are presented in the form of curve 6 in figure 1.

The integral of the normalized Fourier amplitudes S (log f), calculated in the interval between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration

log (f ₂ / μm ^-1 ) = 3 is 0.04.

Reference Example 7

In this example, a polycarbonate substrate with an area of 35 × 35 mm ² and a thickness of 1 mm was applied for subsequent spraying onto it a layer of aluminum with a thickness of 100 nm. After that, the sample was treated in distilled water at 100 ° С for 3 min, then washed in distilled water at room temperature for 30 s and dried in an oven at 80 ° С for 1 h.

Next, a gold layer approximately 100 nm thick was sprayed onto the sample treated in this way. Then, this sample was exposed for 24 h in a state of immersion in a solution of n-decantiol in ethanol (1 g / l) at room temperature in a closed vessel, and the coating was washed and finally washed with ethanol and dried.

The static contact angle of the water droplet located on such a surface is 147 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl does not roll off it.

The topography of this surface was described and investigated in the same way as described above in section "1. Determination of surface topography", and the obtained measurement data are presented in the form of curve 1 in figure 2.

The integral of the normalized Fourier amplitudes S (log f), calculated in the interval between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration

log (f ₂ / μm ^-1 ) = 3 is 0.39.

Example 8

In this example, a prototype was obtained analogously to example 7, with the difference, however, that the thickness of the deposited layer of gold was 50 nm.

The static contact angle of the water droplet located on such a surface is 154 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl rolls off it.

The topography of this surface was described and investigated in the same way as described above in section "1. Determination of surface topography", and the obtained measurement data are presented in the form of curve 2 in figure 2.

The integral of the normalized Fourier amplitudes S (log f), calculated in the interval between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration

log (f ₂ / μm ^-1 ) = 3 is 0.53.

Reference Example 9

In this example, an A1Mg ₃ plate polished with finishing rolls with an area of 35 × 35 mm ² and a thickness of 0.5 mm was degreased with distilled chloroform. Then, the sample was processed in distilled water at 100 ° С for 20 s. Then it was washed in ethanol and dried for 1 h in an oven at 80 ° С.

Next, a layer of gold approximately 50 nm thick was sprayed onto the sample treated in this way. Then, this sample was exposed for 24 h in a state of immersion in a solution of n-decantiol in ethanol (1 g / l) at room temperature in a closed vessel, and the coating was washed and finally washed with ethanol and dried.

The static contact angle of the water droplet located on such a surface is 130 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl does not roll off it.

The topography of this surface was described and investigated in the same way as described above in section "1. Determination of surface topography", and the obtained measurement data are presented in the form of curve 3 in figure 2.

The integral of the normalized Fourier amplitudes S (log f), calculated in the interval between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration

log (f ₂ / μm ^-1 ) = 3 is 0.15.

Reference Example 10

In this example, a monocrystalline Si (100) plate polished by finishing rolls by electro-beam sputtering at a temperature of 520 K was successively coated with an HLHL substrate (H = LaF ₃ , L = MgF ₂ ). Moreover, layers H had a thickness of 100 nm, and layers L 116 nm. This technology is consistent with that described in S. Jakobs, A. Duparre and H. Truckenbrodt, Applied Optics 37, p. 1180 (1998).

Next, a layer of gold approximately 50 nm thick was sprayed onto the sample treated in this way. Then, this sample was exposed for 24 h in a state of immersion in a solution of n-decantiol in ethanol (1 g / l) at room temperature in a closed vessel, and the coating was washed and finally washed with ethanol and dried.

The static contact angle of the water droplet located on such a surface is 120 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl does not roll off it.

The topography of this surface was described and investigated in the same way as described above in section "1. Determination of surface topography", and the obtained measurement data are presented in the form of curve 1 in figure 3.

The integral of the normalized Fourier amplitudes S (log f), calculated in the interval between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration

log (f ₂ / μm ^-1 ) = 3 is 0.10.

Reference Example 11

In this example, a prototype was obtained analogously to example 10, with the difference, however, that in the above sequential deposition of layers instead of (HL) ² , (HL) ^{8 was used} .

The static contact angle of the water droplet located on such a surface is 130 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl does not roll off it.

The topography of this surface was described and investigated in the same way as described above in section "1. Determination of surface topography", and the obtained measurement data are presented in the form of curve 2 in figure 2.

The integral of the normalized Fourier amplitudes S (log f), calculated in the interval between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration

log (f ₂ / μm ^-1 ) = 3 is 0.23.

Example 12

In this example, a prototype was obtained in the same way as described in unpublished application DE 19935326.3. The cycle {SiO (CH ₃ ) [(CH ₂ ) ₂ Si (OH) - (CH ₃ ) ₂ } ₄ (hereinafter referred to as D4-silanol) was obtained in the same manner as described in the application DE 19603241.

4.1 g of AEROSIL ^® 812 (manufactured by Degussa) were dispersed in 28.5 g of 1-methoxy-2-propanol, 5.0 g of D4-silanol and 6.5 g of tetraethoxysilane. To this dispersion was added 1.1 g of 0.1N. p-toluenesulfonic acid and the mixture was stirred for 1 h at room temperature. Then, the obtained lacquer solution was coated on a glass plate using a film drawing frame to form a wet film layer 120 μm thick as a result. After evaporation of the volatile components at room temperature, the resulting coating was cured for 1 h at 130 ° C in an air circulation oven.

Next, a layer of gold approximately 50 nm thick was sprayed onto the sample treated in this way. Then, this sample was exposed for 24 h in a state of immersion in a solution of n-decantiol in ethanol (1 g / l) at room temperature in a closed vessel, and the coating was washed and finally washed with ethanol and dried.

The static contact angle of the water droplet located on such a surface is 165 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl rolls off it.

The topography of this surface was described and investigated in the same way as described above in section "1. Determination of surface topography", and the obtained measurement data are presented in the form of curve 1 in figure 4.

The integral of the normalized Fourier amplitudes S (log f), calculated in the interval between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration

log (f ₂ / μm ^-1 ) = 3 is 0.71.

Example 13

In this example, a test sample was obtained analogously to example 12, with the difference, however, that instead of 1.1 g of p-toluenesulfonic acid, 2.3 g of HCl was added.

The static contact angle of the water droplet located on such a surface is 157 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl rolls off it.

The topography of this surface was described and investigated in the same way as described above in section "1. Determination of surface topography", and the obtained measurement data are presented in the form of curve 4 in figure 4.

The integral of the normalized Fourier amplitudes S (log f), calculated in the interval between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration

log (f ₂ / μm ^-1 ) = 3 is 0.60.

Example 14

Getting a back print (negative)

In this example, a reverse imprint (negative) was obtained using a polymer solution, which serves as a form for obtaining the desired ultrafobic surface. As such a form, the surface obtained in Example 1 was used.

The surface of the mold was poured with a 30% solution of the polymer in methylene chloride, which was used as a copolymer of polymethylmethacrylate and perfluorooctadecylmethacrylate (- [CH ₂ -C (COOCH ₃ ) CH ₃ ] _n - and - [CH ₂ -C (COOC ₁₈ F ₃₇ ) CH ₃ ] _m - at a ratio of n / m = 10; 50 wt.% Solution in butanone), resulting in a coating film in the form of a film with a thickness of approximately 20 μm using a frame for drawing out. After drying at room temperature, a strip 10 mm wide was cut out of the film with a scalpel, reinforced by gluing the adhesive film on the upper side and separated from the mold.

A layer of gold about 50 nm thick was sprayed onto the lower (i.e., initially facing the form) side of the film. Then, the n-decantiol was sprayed at room temperature in a closed vessel for 24 h with a coating for 24 h and finally washed with ethanol and dried.

The static contact angle of the water droplet located on such a surface is 165 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl rolls off it.

Example 15

Obtaining an ultra-phobic surface from a reverse print (negative)

In this example, the desired ultraphobic surface was obtained using a polymer solution using negative. As such a negative, the surface obtained in Example 1 was used.

Stage 1: Obtaining a reverse print, which serves as a form for obtaining an ultrafobic surface

The mold surface was poured with a 50 wt.% Solution of bisphenol A polycarbonate A (M _n = 1000) in methylene chloride, and a film-like coating was used to form a coating in the form of a film with a thickness of approximately 100 μm.

After drying at room temperature, a strip 20 mm wide was cut out from the film with a scalpel, reinforced by gluing the adhesive film on the upper side and separated from the mold.

A layer of gold about 50 nm thick was sprayed onto the lower (i.e., initially facing the form) side of the film. Then, a 24-hour exposure to this gold layer of a sample with a few drops of a solution of n-perfluorooctantiol in α, α, α-trifluorotoluene (1 g / l) was coated at room temperature in a closed vessel and finally washed with α, α, α-trifluorotoluene and dried.

Stage 2: Obtaining from the inverse of the desired ultrafobic surface using a polymer mixture containing an oleophobic polymer as an additive

The surface of the mold was poured with a 30% solution of the polymer mixture in polystyrene methylene chloride (M _n = 15000) and approximately 10 wt.% Copolymer of polymethyl methacrylate and perfluorooctadecyl methacrylate (- [CH ₂ -C (COOCH ₃ ) CH ₃ ] _n - and - [CH _2- C (COOC ₁₈ F ₃₇ ] _m -; ratio n / m = 10) to obtain a coating in the form of a film in the form of a film with a thickness of approximately 20 μm After prolonged drying at room temperature (for approximately 10 hours), the film was cut out with a scalpel, a strip 10 mm wide, from the upper side it was strengthened by sticking an adhesive tape and separated from Orma.

A layer of gold about 50 nm thick was sprayed onto the lower (i.e., initially facing the form) side of the film. Then, a coating with a 24-hour exposure was sprayed with n-decantiol at room temperature in a closed vessel, then washed with ethanol and dried.

The static wetting angle of the water droplet located on the surface thus obtained is 164 °. When the surface tilts at <10 °, a drop of water with a volume of 10 μl rolls off it.

The table presents in a systematic form the results obtained in the examples according to the invention and in comparative examples.

It is unambiguously obvious that for ultrafobic surfaces for which the contact angle of the water droplet located on the surface exceeds 150 °, the integral of the curve a (f) · f = S (log f) calculated between the lower integration limit log (f ₁ / μm ^-1 ) = -3 and the upper limit of integration log (f ₂ / μm ^-1 ) = 3, higher or equal to 0.5. The edge angle of such an ultra-phobic surface obtained from the inverse print, as well as the edge angle of the negative exceeds 150 °.

Claims (26)

1. A structured (profiled) surface with ultra-phobic properties, characterized in that it has a topography in which the relationship between the spatial frequencies f of individual Fourier components and their amplitudes a (f) is determined by the function S

whose integral, calculated between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration log (f ₂ / μm ^-1 ) = 3, is at least 0.5, and the specified surface is made of hydrophobic or primarily from an oleophobic material, or has a coating of such a hydrophobic or especially oleophobic material. 2. The ultra-phobic surface according to claim 1, characterized in that the integral of the function S exceeds 0.6. 3. The ultra-phobic surface according to claim 1 or 2, characterized in that it has a contact angle of at least 150 ° and a rolling angle of less than 10 °. 4. Ultra-phobic surface according to any one of claims 1 to 3, characterized in that it has a contact angle of at least 155 °. 5. Ultra-phobic surface according to any one of claims 1 to 4, characterized in that it is made of metal or plastic. 6. The ultrafobic surface according to claim 5, characterized in that the metal is selected from the group comprising beryllium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, gallium, yttrium, zirconium , niobium, molybdenum, technetium, ruthenium, rhenium, palladium, silver, cadmium, indium, tin, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium , tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, primarily titanium, aluminum, magnesium and neither cell or corresponding alloy of the named metals 7. The ultra-phobic surface according to claim 5, characterized in that the metal is an alloy of aluminum and magnesium, primarily A1Mg ₃ . 8. The ultra-phobic surface according to claim 5, characterized in that duroplast or thermoplastic is selected as the plastic. 9. The ultra-phobic surface of claim 8, wherein the duroplast is selected from the group consisting of diallyl phthalate resin, epoxy resin, urea-formaldehyde resin, melamine-formaldehyde resin, melamine-phenol-formaldehyde resin, polymeric silicone, and polymeric resin a group comprising a thermoplastic polyolefin, for example polypropylene or polyethylene, polycarbonate, polyester carbonate, polyesters, for example PBT or PET, polystyrene, styrene copolymer la, a copolymer of styrene and acrylonitrile, styrene graft copolymer kauchuksoderzhaschy, for example acrylonitrile-butadiene-styrene (ABS), polyamide, polyurethane, polyphenylene sulphide, polyvinyl chloride or any possible mixtures of said polymers. 10. An ultrafobic surface according to any one of claims 1 to 9, characterized in that a layer of a hydrophobic auxiliary phobic agent, primarily an anionic, cationic, amphoteric or nonionic surfactant, is applied to this surface. 11. Structural material or building material having an ultra-phobic surface according to any one of claims 1 to 10. 12. Ultra-phobic surface according to any one of claims 1 to 10, characterized in that it is designed to reduce the frictional force of the lining of vehicle bodies, aircraft fuselages and ship hulls. 13. Ultra-phobic surface according to any one of claims 1 to 10, characterized in that it is intended for use as self-cleaning coatings or cladding of buildings, roofs, windows, ceramic building materials used, for example, for plumbing equipment and household appliances . 14. Ultra-phobic surface according to any one of claims 1 to 10, characterized in that it is intended for use as an anti-corrosion coating of metal products. 15. Ultra-phobic surface according to any one of claims 1 to 10, characterized in that it is intended to be used as a transparent panel or as a transparent layer applied to transparent glasses, especially quartz or polymer glasses, primarily for solar panels, transport funds or greenhouses. 16. A method of obtaining a surface with ultrafobic properties according to any one of claims 1-10 based on AlMg ₃ alloy, characterized in that this surface is cleaned, etched, subjected to anodic oxidation, passivated in boiling water, if necessary, applied to it, first of all by sputtering, a layer of a noble metal as an adhesion promoter, primarily of gold, with a thickness of 10 to 100 nm and finally coated with a hydrophobic material, primarily anionic, cationic, amphoteric or nonionic surface-active compound as using auxiliary phobic agent. 17. A method of producing a surface with ultra-phobic properties, characterized in that a mold is made that is an inverse imprint of the ultra-phobic surface with the required topography, using for this purpose a mixture of plastic and a hydrophobic or, first of all, oleophobic additive, which during curing is deposited in the form of a thin film between mold surface and molded plastic product. 18. A method of obtaining a surface with ultrafobic properties, characterized in that the ultrafobic surface with the desired structure is formed using plastic, especially duroplast or thermoplastic, and if necessary, an adhesion promoter layer is applied to the surface of the molded product obtained in this way from the inverse print and then coated with a hydrophobic or primarily oleophobic material. 19. The method according to p. 18, characterized in that the polymer used is a hydrophobic polymer, preferably a copolymer of polymethylmethacrylate and perfluorooctadecylmethacrylate, and it does not require the additional coating of a hydrophobic or oleophobic material. 20. The method according to 17 or 18, characterized in that as the shape with the inverse print, respectively obtained from this inverse of the surface with the desired structure, use the surface subjected to etching, anodized and treated with hot water with a temperature in the range from 50 to 100 ° C and containing mainly aluminum or aluminum alloy. 21. The method according to p. 17 or 18, characterized in that a microstructured, anodized, calcined and containing mainly aluminum or aluminum alloy surface is used as the shape with the inverse print, respectively obtained from this inverse of the surface with the desired structure. 22. The method according to any one of paragraphs.17-21, characterized in that as a plastic for the formation of the surface used duroplast or thermoplastic. 23. The method according to p. 22, characterized in that as a duroplast, one is used selected from the group including diallyl phthalate resin, epoxy resin, urea-formaldehyde resin, melamine-formaldehyde resin, phenol-formaldehyde-resin-resin-resin-resin. 24. The method according to item 22, wherein the thermoplastic used is one selected from the group consisting of a thermoplastic polyolefin, for example polypropylene or polyethylene, polycarbonate, polyester carbonate, polyesters, for example PBT or PET, polystyrene, styrene copolymer, styrene copolymer and acrylonitrile, a rubber-containing grafted copolymer of styrene, for example a copolymer of acrylonitrile, butadiene and styrene (ABS plastic), polyamide, polyurethane, polyphenylene sulfide, polyvinyl chloride or any possible mixture of these polymers. 25. The method according to any one of paragraphs.17-24, characterized in that the surface obtained from the reverse imprint of the molded product is coated using an auxiliary hydrophobic phobic agent, especially an anionic, cationic, amphoteric or nonionic surfactant, or use such auxiliary phobic agent as an additive to compatible polymers, which imparts hydrophobic properties to the surface. 26. A method of testing surfaces for their ultraphobic properties, characterized in that a surface of noble metal or GaAs is applied to the surface, primarily by spraying, as an adhesion promoter, primarily from gold, with a thickness of 10 to 100 nm, then coated with a layer of auxiliary phobic an agent, preferably decantiol, after which the surface topography is examined, primarily using scanning tunneling microscopy, scanning atomic force microscopy and white light interference interferometry in combination, based on the obtained measurement data define the spatial frequencies f and the amplitude of their structures and (f), and the integral of the function S

calculated between the lower limit of integration log (f ₁ / μm ^-1 ) = - 3 and the upper limit of integration log (f ₂ / μm ^-1 ) = 3.

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