MXPA01002432A - Textile articles or clothing having super hydrophobic coating - Google Patents

Abstract

The present invention relates to textile articles and clothing such as outdoor garments, indoor garments exposed to aqueous liquid, swim wear, leather, hats, textile sun roofs for cars, sun blinds or awnings which have at least part of their surface provided with super hydrophobicity.

Description

TEXTILE ARTICLES OR GARMENTS THAT HAVE SUPERHYDROPHOBIC COATING FIELD OF THE INVENTION The present invention relates to textile articles and garments such as outer garments, undergarments exposed to aqueous liquid, bathing suits, shoes, leather, hats, textile awnings for automobiles, sun blinds or canopies having at least part of its surface provided with superhydrophobic character.

BACKGROUND OF THE INVENTION For example, US Patent No. 3,498,527 teaches that paperboard cartons for liquids can be waterproofed by application of a waterproof coating such as wax or polyethylene, and a similar method is shown in the US patent. No. 2,708,645 for paper cups for drinking waterproof and in US Patent No. 3,212,697 for paper bags for food. In U.S. Patent No. 3,597,313, the temporary moisture resistance is imparted to the paper by coating it with a reaction product of polymeric aldehyde-polymeric alcohol.

The coating procedures, by themselves, have been used to produce disposable articles of sanitary garments. In U.S. Patent No. 3,078,894, a disposable sanitary towel is described consisting of an adsorbent layer having a liquid repellent reinforcement of polyvinyl alcohol or similar material capable of initially repelling water, but gradually solubilizing. The degree of water repellency, therefore the life time of the towel, is controlled by varying the thickness of the reinforcement. Because the necessary life of the towel can not be predicted by the manufacturer or user, the reinforcement must be sufficiently thick to take into account all normal contingencies. U.S. Patent No. 3,542,028 relates to a sanitary napkin which can be discarded by the toilet consisting of a cellulosic sheet treated with a fluoropolymer coating. U.S. Patent No. 3,559,650 discloses the preparation of a sanitary napkin having two disposable sides by the toilet separated by a very thin waterproof film to hold once both sides of the towel have been disintegrated upon discarding. Analogous to the process of coating a surface with a waterproof substance is the concept of reacting a surface with another material in order to form a reaction product on the surface having water repellent properties. For example, US Patents Nos. 2,130,212 and 3,137,540 show that materials such as polymeric alcohols can be reacted with other materials to increase their water repellent properties. The last IsteáTs ^ is the patent teaches the treatment of polyvinyl alcohol articles with an aqueous emulsion of an aldehyde to impart water repellency to them. U.S. Patent No. 3,626,943 demonstrates that disposable diapers can be made of polyvinyl alcohol and water-proof on one side 5 by reaction with formaldehyde. These reaction type coating processes have certain disadvantages. They are carried out in the aqueous phase which is complicated and require relatively large amounts of reagents. Most procedures that employ some form of chemical reaction in situ to produce a repellent surface Water is carried out in the liquid phase, some steam phase treatments are presented in U.S. Patent Nos. 2,306,222; 2,961, 388; and 3,017,290. A known method of water-repellent and oil-repellent finishing of textiles, described in US Pat. No. 1, 158,634, includes treatment with plasma in a luminescent discharge in an atmosphere of inorganic gases, followed by treatment with an acrylic monomer containing fluorine in the gas phase. Another prior method for achieving plasma polymerization of the film, described in US Patent No. 4,188,426, includes treatment in a luminescent discharge of per-fluoro-cyclo-butane or hexafluoroethane to reduce the coefficient of friction and improve hydrophobicity of surface of organic and inorganic textile substrates (for example, polyethylene films, metals). However, these descriptions do not achieve a level of water repellency as the present invention.

Frequently, fluorocarbon coatings deposited with plasma are cited in the literature as "Teflon-type coatings" because their composition CFx (0 <x <2) and their surface energy can be made very close to that of polytetrafluoroethylene (PTFE). , - (CF2-CF2- 5) n), known in the market as Teflon®. Methods of plasma coating metals, polymers, and other textile substrates with fluorocarbon films are known in the art. As an example, it is known from the US patent 4,869,922 and from other sources, that the deposition of luminescent discharges radio frequency (RF) continuous (ie, unmodulated) fed with fluorocarbons provides films, layers, tapes, plates, and articles of different shapes made of plastic, metal or other materials, with a thin fluorocarbon coating, without any other material interposed between the coating itself and the substrate. It is said that said coatings have very good adhesion to processed articles, to be free of vacuum, to be uniform or non-porous, and to present controlled humectant character characteristics, which depend on the chemical composition of their surface. The continuous, non-modulated plasma process of the aforementioned patent leads to coatings characterized by values of contact angle with static water (WCA) less than 120 °. Luminescent discharge treatments are also contemplated in US-A-5 462 781 to improve the binding capacity of an implantable polymer medical device or to change the capacity of r-mi r ^^^^^^. ^^ jl ^ jj ^ l í y: ^. . - A. ^^ Moistening a polymeric fabric. Some of the references discussed in this patent confirm continuous, unmodulated plasma treatments as a means to vary the inherent WCA of a surface. US-A-5 034 265 describes a continuous, non-modulated plasma treatment to improve the biocompatibility of vascular grafts with a fluorocarbon CFX coating deposited on the inner wall of the grafts in a suitable plasma reactor fed with tetrafluoroethylene (C2F4) TFE) at 0.2 Torr. In the preferred embodiment of the invention, no other material is interposed between the substrate and the coating. US Patent No. 5,328,576 describes a method for imparting water and oil repellent surface properties of fabrics or paper that includes pretreatment in a low pressure oxygen plasma in the presence of water vapor followed by plasma polymerization of methane in a high-frequency luminescent discharge that takes place in the same treatment chamber. This method does not provide permanent, durable coatings with a WCA higher than approximately 120 °. U.S. Patent No. 5,262,208 discloses a gaseous plasma treatment for the preservation of paper manuscripts filed by a thin film protective polymer film. Time of treatment is on the scale of 30-3600 seconds. Other methods have been used to obtain thin coatings on mesh materials with short treatment periods. The provision of surface treatment is described in US Patent No. 4,842,893 and 4,954,371 which discloses a process for high-speed coating of substrates, with a complete and uniform adhesion layer and by radiation beam curing of the monomers deposited in steam for multi-layer capacitors. U.S. Patent No. 4,842,893 discloses a high speed coating process including flash system and electronic beam cure. Both descriptions of the electronic beam are incorporated herein by reference. Other uses of electronic beam coatings in the field of the electronics industry have been reported by the 10 Westinghouse science and technology center in the USA (Adv. Mat. Newsletter Volume 13, No 9, 1991 page 4). It has now been found that providing at least part of the surface of textiles with a hydrophobic character at levels that have hitherto been unattainable can provide a very important benefit for the use of said textiles.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to textile articles or garments hereinafter referred to as textiles, such as outer garments, interior fabrics that are exposed to aqueous liquid such as bed mattresses, rugs, bath mats or the like, swimsuits, shoes, leather, hats, awnings automotive textiles, shutters t.for the sun or canopies that have at least part of the surface treated to be superhdrof g 2a. In particular, the present invention relates to textiles that are coated by plasma deposition of fluorocarbons. Specifically, the present invention, having the characteristics mentioned in the appended claims, refers to textiles having at least part of its surface coated with a thin, non-porous, fluorocarbon coating of good adhesion with superhydrophobic properties, i.e. , characterized by angle values contact with static water (WCA), measured on a smooth, flat surface, of more than about 120 °, preferably of more than 130 °, most preferably of more than 150 °. For example, textiles that are treated with this method have their hydrophobic character remarkably improved. They can, for example, provide improvements in water repulsion, prevention of dirt / stain adhesion, reduced buildup on the surface or not being harmful to water / air vapor permeability. The present invention relates to textiles having their surface treated, that is characterized by values of contact angle with static water (WCA) of more than about 120 °, preferably of more than 130 °, most preferably greater than 150 °. The textile substrates of interest for the present invention can include a wide variety of materials in the form of meshes, tapes, films, leather or fur of the animal skin type, woven and nonwoven layers; they may be porous or non-porous, rigid or flexible, made of polymers, natural or synthetic fibers, leather, biodegradable materials, or any conventional material used in the manufacture of textiles or products comprising textiles for outdoor use. When organic synthetic resins are selected, said substrate materials can be made of polyethylene, polyacrylics, polypropylene, polyvinyl chloride, polyamides, polystyrene, polyfluorocarbon polyurethanes, polyesters, silicone rubber, hydrocarbon rubbers, polycarbonates and other synthetic polymers. A particularly preferred polymeric substrate is polyethylene or polypropylene as used, for example, in the manufacture of nonwoven textile substrates. The textiles are preferably subjected to a modulated luminescent discharge plasma treatment which is carried out with a vapor compound or fluorocarbon gas fed into a suitably configured reaction vessel in which the textiles are placed. The plasma process deposits a thin film of fluorocarbon, continuous with superhydrophobic surface characteristics, tightly bound to the surface of the textiles. Alternatively, a conventional thin film coating process followed by high energy surface cure may be used. This is the method in which a high speed vacuum coating process is used to produce thin and durable water repellent coating on a substrate g ijg tex itsi '% Use, for example, a mobile support such as a rotating drum in faith * * a vacuum chamber The surface of the support is kept at a temperature sufficient to allow condensation of a vaporized material deposited in the The material is a curable monomer with a relatively low molecular weight.The monomer vapor is created using an instant vaporizer.The desired amount of curable monomer is introduced into a heated flash system where the material is vaporized. it is transported, for example, by its inherent pressure, to the remaining textile substrate in the rotating drum and condensed on the surface of the textile substrate. According to the method, the textile substrate is transported to a curing medium such as an energy source that emits an electronic beam, UV light radiation or exposure to an electromagnetic field. Alternatively, the curable monomer can also be transferred into radicals by passing through a plasma zone (area of high voltage discharge). The curing of the monomer by the curing medium provides a coating on the surface of the textile substrate having a contact angle with static water of more than 120 °. The method for delivering the curable monomer to the textile substrate to keep the amount of monomers to a minimum can use a Ultrasonic atomizer that produces microdrops of curable monomer. They are released in a vaporization tube heated by band heaters. The atomized drops collide on the inner wall of the vaporization tube and vaporize instantaneously, that is, flash (flash). This reduces the opportunity for polymerization before being deposited * on the textile substrate. In one aspect of the present invention, the textile substrate can be water repellent on one side only or alternatively be repellent on both sides. "Plasma", as used herein, is used in the sense of "low temperature plasma" or "cold plasma" produced by initiating a luminescent discharge in a low pressure gas through energy supply. Luminescent discharges contain a variety of species Chemically active and energetic enough to cause chemical reactions are exposed surfaces, that is, covalent binding to a suitable substrate material. Cold plasmas, or luminescent discharges, are usually produced with high frequency energy supply (from KHz to MHz and GHz) (HF plasmas). Electrons, positive and negative ions, atoms, excited molecules, free radicals, and photons of various energies are formed in a cold plasma. "Modulated plasma" means a non-continuous plasma, HF plasma, that is, a luminescent discharge confers ejected impulse energy between a maximum and zero value (On / Off pulse) or a fraction thereof, at a certain frequency, with a suitable pulse generator connected to the main power supply. In the case of pulse on / off systems, the time on and time off values are within the experimental parameters of the procedure. Overlaying ^ uri pulse on / off drive to the main field of high frequency that generally pulses: -ai (* | pa! * luminescent discharge, alternating short continuous discharges with plasma shutdown time intervals where the active species still They exist in the gas phase, but the effects of ions and electrons are strongly reduced.This alternative exposure to two different procedures leads to unique surface modifications of substrates, which may be very different from those of the continuous plasma process, as will be demonstrated "Deposition with plasma" or "plasma polymerization" is the The plasma process leads to the formation of thin (0.01-2 μm), partially entangled, without hollow, continuous, substantially adherent substrates. The molecules of the gas phase are fragmented by energetic electrons, which are capable of breaking chemical bonds; this procedure leads to radicals and other chemical species that are able to deposit on the surfaces inside the vacuum chamber and form a thin, uniform film. The action of the plasma can also affect the surface of a polymer substrate in the first deposition time; energy species can break bonds in the substrate with the possible release of gas products, such as hydrogen, and the formation of free radical sites that contribute to covalent bonds between the growing film and the substrate. It has been found that it is possible to deposit thin fluorocarbon films with superhydrophobic characteristics, ie, that * $ show a surprisingly high static water contact angle (WCA) value, even at approximately 165 °. The present invention, therefore, relates to agfextiles with fluorocarbon films characterized by a WCA value higher than 120 °, preferably higher than 130 °, still most preferably higher than 150 °. In particular fluorocarbon coatings with an F / C ratio of about 1.50 to about 2.00 deposited on different substrates and characterized by WCA values greater than about 120 °, such as between 155 ° and about 165 °, they are of useful application in textiles , especially if the coatings have been deposited on the surface of different polymer substrates such as polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), in the form of films and / or non-woven fabrics. It should be noted that the F / C ratio can theoretically be up to 3, if the coating would be formed only of a monomolecular layer of CF3 groups. But the formation of intermolecular entanglements and the formation of the claims (containing CF2 fragments) that are inserted on the surface decreases the previous theoretical value so that the coatings obtained, regardless of the fact that they contain many CF3 groups, have a general relationship of F / C on the scale of 1.50 to approximately 2.00. The thickness of the coatings depends on the duration of the plasma procedure at different conditions, and can be maintained between 0.01 and 2 μm. It has been found that the nature of the materials of THAT? The substrate does not influence the chemical composition or thickness of the coatings. Surfaces were obtained with WCA values of up to 165 ° (for example, 165 ° ± 5 °). The textiles to be treated are subjected to gas discharge 5 with plasma modulated in the presence of at least one gas or fluorocarbon vapor. Specifically, fluorocarbon gases or vapors such as tetrafluoroethylene (TFE, C2F), hexafluoropropene (HFP, C3F6), perfluoro- (2-trifluoromethyl-) pentene, perfluoro- (2-methylpent-2-ene), or its trimer can be used. , with TFE being the most preferred choice in the present. The procedure Plasma deposition is preferably carried out by placing the textile in an appropriately disposed plasma reactor, connecting the reactor to a surface of a gas or fluorocarbon vapor, regulating the gas flow and pressure inside the reactor, and holding a luminescent discharge in the reactor with a high frequency electric field in a driven mode (modulated) by an adequately pulsed power supply. The parameters that define the luminescent discharge treatment include the gas or steam fed, its flow velocity, its pressure, the position of the textile inside the reactor, the design of the reactor, the excitation frequency of the power supply, the input supply , the ignition time and the time of shutdown of the pulse system. The textiles can be placed in the "luminescent" region of the discharge, ie directly exposed to the plasma or in the "post-luminescent" region, ie, downstream with respect to the visible luminescence. The two positions generally result in . ^ ^. ^^ - ^^^^^ coatings with different composition and properties; The textile treatment with modulated luminescent discharge also results in different coatings with respect to the continuous treatments.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will now be described, purely by way of example, with reference to the accompanying figures, in which: Figure 1 compares a conventional "continuous" RF luminescent discharge with a "modulated" on / off RF luminescent discharge; Figure 2 shows a typical scheme of a plasma reactor adapted for use within the context of the invention; Figure 3 shows an ESCA C1s signal from a uncoated polyethylene substrate where the signal is due only to C-H, C-C substrate bonds; Figure 4 shows an ESCA signal C1s of a PE substrate coated with a fluorocarbon coating deposited as described in Example 1 (luminescent position, continuous mode), with WCA of 100 ± 5 °; the signal is composed of components due to the CF3, CF2, CF and CCF bonds of the fluorocarbon coating, and to C-H, C-C bonds due to surface contamination; Figure 5 shows a C1 s signal ESCA of a PE substrate coated with a fluorocarbon coating deposited as described in Example 1 (pistol-luminescent position, continuous mode) with a WCA of 120 ± 5 °; the signal is composed of components due to the 5 CF3, CF2, CF and CCF bonds of the fluorocarbon coating, and to C-H, C-C bonds due to surface contamination; and Figure 6 shows a signal C1 s ESCA of a PE substrate coated with a fluorocarbon coating deposited as described in Example 1 (luminescent position, modulated mode), with a WCA of 165 ± 5 °; the signal is composed of components due to the CF3, CF2, CF and CCF bonds of the fluorocarbon coating, and to C-H, C-C bonds due to surface contamination.

DETAILED DESCRIPTION OF THE INVENTION FIG. 1 compares a conventional "continuous" plasma (FIG. 1a) with a modulated method of the invention, (FIG. 1 b) showing pulsating alternating pulsed plasma times with off (ie, without plasma) plasma . The two methods are schematized with reference to their drive signals. The reactor 1 shown schematically in figure 2 was not used exclusively to develop the deposition method object of the present invention. The vacuum chamber of reactor 1 is made of glass * ^^ ^ Í XB? U &S * £ ¡Jk & S & g | > j Ugi '* & It is supplied with an external electrode with RF power 2 and an internal electrode connected to 3"The" external electrode is connected to a power supply 4 (typically a radio frequency generator that operates at, for example 13.56 MHz) through an equilibrium network and an on / off pulse generator 5. The textiles can be treated in the "luminescent" region of the reactor, at the grounded electrode 3, as well as in the "post-luminescent" position, ie in a post-luminescent textile retainer 6. The gas / vapor is fed by an appropriate mass flow meter through a gas / vapor manifold 7 and its pressure, measured at the pumping outlet 8 out of the reactor, it is kept at a certain constant value with a manual valve over the vacuum connection between the reactor and its pumping unit, although the arrangement shown in the drawing represents an actual choice. Preferably, those skilled in the art will immediately recognize that the driven excitation of the plasma reactor can be achieved by different means, such as direct excitation by means of powered RF generators which are commonly used in radar and telecommunication techniques. . Preferably, the deposition process is performed with a radio frequency generator (13.56 MHz). The RF energy 20 supplied to the external reactor electrode is maintained, in the range of 1-500 watts for a power density of 0.02-10 Watt / cm2. The reactor is fed with fluorocarbon compound at a flow rate of 1-100 cm3 / min and maintained at a constant pressure of 50-1000 mTorr during the ^ ... ^^^. ^^^ ^^? ^^^^^ l ^. -. ^^ ÁA ^^^. ^^^^^^ M ^^^^ S? ^^ '- *. process. Preferably, the luminescent discharges are modulated by the image generator, preferably with values of 1-500 ms of on time and 1-1000 ms of off time, the respective values being approximately 10 ms and approximately 190 ms the 5 choice more preferred in the present. The deposition procedure can vary from a few seconds to many hours; during that time a uniform coating of fluorocarbon is deposited on substrates placed in the luminescent region as well as on those in the post-luminescent region. The deposition rate was measured, being a typical in the range of 20 - 10 400 A / min, weighing (weight / time) the textiles before and after the discharge or measuring the thickness of the coatings (thickness / time) with a Alpha Step rugosimeter. The rate of position and chemical composition of the coating depends on the experimental conditions (pressure, power, position of the substrate, time on, time off, gas supply and flow rate) of the discharge. The coatings obtained are uniform over the entire surface of the substrate; when they are deposited on flat (ie flat) substrates, smooth, their hydrophobic character has been estimated by their static WCA value, measured with a WCA goniometer. The revision is made on a flat, ie flat, smooth surface of a substrate after coating. The term "smooth," as used herein for measurements at contact angles with water, refers to a roughness of no more than five microns according to typical rugosity measurements on continuous surfaces.

WCA values have been measured in the range of about 120 ° to about 165 °, corresponding to a critical surface tension less than that of PTFE (18 dynesibrn) for CFx fluorocarbon coatings, when x ranges from about 1.50 to about 2.00. The chemical composition of the coatings is determined preferably by electronic spectroscopy for chemical analysis (ESCA) giving a depth of sampling of the technique (approximately 100 Á). The adhesion of the coating to the substrate is very good. The following examples are given for the purpose of better illustrating the inventive concept of the present invention, and to emphasize the advantages of using modulated treatments compared to continuous treatments.

EXAMPLE 1 Three flat and flat silicon, PE and PP substrates with areas in the range of 2-10 cm2 per material were placed on the electrode 3 connected to the reactor ground shown in Figure 2. A similar set was placed. of substrates in the post-luminescent position in 6. The C2F was adjusted to continuously feed the reactor to 6 cm3 / min, and adjusted the pressure to 300 mTorr. The RF generator was connected to the reactor and the discharge was sustained with 50 watts of input power for 90 minutes, then disconnected.

Another luminescent discharge was subsequently conducted with a similar set of substitions placed in the luminescent position and without substrates in the post-luminescent position, under the same conditions as described above, except for the fact that the modulation was carried out at 10 ms of ignition time and 190 ms shutdown time using the pulse generator. At the end of the two discharges, the substrates were removed from the reactor and their WCA was measured. The WCA values shown in Table 1 were found, which are compared with the WCA values of the unprocessed substrates. A deposition rate of 30 ± 5 A / min was measured for coatings deposited in the modulated mode. Other substrates, treated in both modes, were analyzed with the ESCA technique. This surface composition turned out to be entirely composed of carbon and fluoride (fluorine as element), according to the results shown in tables 2a-c. No other elements were detected (for example Si for silicon substrates), which means that the coatings are continuous. In Figure 3, the spectrum C1 s of the uncoated PE substrate is shown, while in Figures 4, 5 and 6, respectively, its spectra C1s of the PE samples coated as described above. i &i TABLE 1 TABLE 2a Results of ESCA for continuous discharge (luminescent position) of example 1 fifteen TABLE 2b Results of ESCA for continuous discharge (post-luminiscerf) from Example 1 TABLE 2c ESCA results for the modulated discharge (luminescent position) of example 1 These examples were made on smooth and flat surfaces for laboratory convenience and WCAs measurement. The respective textile surface, for example, if it is fibrous has an apparent WCA that differs from the flat and smooth surface WCA due to the surface texture. However, the microscopic surface behavior due to the coating is not different from flat, smooth fibers.

:, As an alternative to provide the textile substrates of the present invention, the method of thin film coating with a monomer followed by surface curing can be used. The coating formed by the method of the present invention has a thickness of less than 5 microns, and preferably less than 2 microns and still very preferably in the range of 0.001 to 1 microns. The coatings are formed by deposition of a curable monomer vapor, under vacuum, on a mobile textile substrate that is mounted in thermal contact with a support, for continuous processing preferably a rotating drum, which is maintained at a temperature below the boiling point of the vaporized monomer under ambient conditions in the vacuum chamber. As a result of this temperature difference, the monomer vapor condenses on the surface of the textile substrate. The monomer materials used in the present invention are of weight Relatively low molecular weight, between 150 and 1000 Atomic Mass Units (AMU), and preferably on the 200 to 300 AMU scale. Polyfunctional fluorocarbons and especially fluoroacrylates or mixtures of monofunctional fluoroacrylates and polyfunctional fluoroacrylates are preferred. The monomers or mixtures of monomers used have an average of around two or more double bonds (i.e., a plurality of olefinic groups) and have a vapor pressure to condense on the surface of the textile substrate. Said vapor pressures are for example at a pressure between 1.33 10 ~ 6 mbar and 1 33 10"1 mbar, most preferably a vapor pressure of about 1.33 1 I 0 or 2 mbar at standard temperature and pressure, (i.e. "relatively low boiling materials." These high vapor pressure monomers can be vaporized instantaneously at low temperatures and therefore are not degraded (fractured) by the heating process.The absence or low amount of non-reactive degradation products it results in coatings with reduced levels of volatile components wherein substantially all of the deposited monomer is reactive and will cure to form an integral film when exposed to a radiation source.

These properties make it possible to provide a substantially continuous coating despite the fact that the deposited film is very thin. The cured films exhibit excellent adhesion and are resistant to chemical attack of organic solvents and inorganic salts. The high speed vacuum coating procedure for Producing water vapor permeable textile substrates with exceptional water repellent properties requires a curable monomer component. Conveniently, the curable monomer for obtaining water repellent coatings comprises a group containing fluoro. In one embodiment, any useful fluoromonomer can Used, including, but not limited to, fluoroacrylate monomers, fluoroolefin monomers, fluorostyrene monomers, fluoroalkylene oxide monomers (eg, perfluoropropylene oxide, perfluorocyclohexene oxide), fluorinated vinyl alkyl ether monomers, and the like.

Stk ^ * ^ * Sa + ^^ m ^ L .. ^ *? ^ * ¡** á «Á. . The compounds of the present invention are copolymers thereof with suitable comonomers, wherein the comonomers are fluorinated or non-fluorinated. Fluoromonomers that are polymerized by a free radical polymerization process are preferred. In one embodiment, fluorinated fluorostyrenes and vinylalkyl ether monomers that can be used in the method of the present invention include, but are not limited to, α-fluorostyrene; β-fluorostyrene; a, β-difluorostyrene; β, β-difluorostyrene; a, β, β-trifluorostyrene; α- trifluoromethylstyrene; 2,4,6-Tris (trifluoromethyl) styrene; 2,3,4,5,6-10 pentafluorostyrene; 2,3,4,5,6-pentafluoro-α-methylstyrene; and 2,3,4,5,6-pentafluoro-β-methylstyrene Still in another embodiment, tetrafluoroethylene can be used in the method of the present invention and includes, but is not limited to, tetrafluoroethylene-hexafluoropropylene copolymers, ether copolymers tetrafluoroethylene-15-perfluorovinyl (for example, copolymers of tetrafluoroethylene with perfluoropropylvinyl ether), tetrafluoroethylene-ethylene copolymers, and perfluorinated ionomers (for example, perfluorosulfonate ionomers; perfluorocarboxylate ionomers). In another embodiment, the fluorocarbon elastomers (for example, see 7 Encyclopedia of Polymer Science &Engineering 257) are a group of fluoroolefin polymers that can also be used in the process of the present invention and include, but are not limited to, , poly (vinylidene fluoride-co-hexafluoropropylene); poly (vinylidene fluoride-co- lteíi¿fe- ^ - sh *. B¡ s ^ ñ ^ ¡-i * Í &.: ^ Hexafluoropropylene-co-tetrafluoroetjlerio); polyfvinylidene fluoride-co-tetrafluoroethelan-co-perfluoro (methyl vinyl ester)]; poly [tetrafluoroethylene-co-perfluoro (methylvinyl ether)]; poly (tetrafluoroethylene-co-propylene; and poly (vinylidene fluoride-co-chlorotrifluoroethylene). In the preferred embodiment, due to their reactivity, physical properties and properties of cured films formed from said components, fluoroacrylates are monomeric materials. particularly useful The term "fluoroacplato monomer", as used herein, refers to esters of acrylic acid (H2C = CHCOOH) or methacrylic acid (H2C = CCH3-COOH), in which the esterification group is a fluorinated group such as perfluoroalkyl. A specific group of fluoroacrylate monomers in the method of the invention are compounds represented by the formula (I) H2C = CR? -COO (CH2) n R2 (I), wherein n is 1 or 2; R1 is hydrogen or methyl; and R2 is a perfluorinated aromatic group Or perfluorinated aliphatic such as saturated or unsaturated, linear or branched, perfluorinated alkyl, phenyl or naphthyl of C1 to C10. In a particular embodiment of the invention, R2 is a perfluoroalkyl of C1 to Ce or -CH2-NR3 -S02-R4, wherein R3 is C2 alkyl and R is perfluoroalkyl of C-i to C8. The term "perfluorinated", as used herein, means that all or essentially all of the hydrogen atoms on an organic group are replaced with fluorine. Illustrative monomers of formula (I) above, and their abbreviations include the following: & ¡H. 2- (N-eylperfluorooctansulfonamido) ethyl acrylate ("EtFOSEA"); methacrylate ele 2- (N-ethylperfluooctansulfonamido) ethyl ("EtFOSEMA"); 2- (N-methylperfluorooctansulfonamido) ethyl acrylate ("MeFOSEA"); 2- (N-methylperfluorooctansulfonamido) ethyl methacrylate ("MeFOSEMA"); 1, 1-Dihydroperfluorooctyl acrylate ("FOA"); and 1,1-Dihydroperfluorooctyl methacrylate ("FOMA"). Alternatively, the curable monomer component may also include polyfunctional acrylates, which are set forth in the U.S.A. 4,842,893.

BENEFITS OF THE PRESENT INVENTION Without attempting to be limited by theory, it is believed that the benefits of the present invention can be obtained by the mechanism indicated below. Textiles according to the present invention typically provide several functions. For one they are protectors for the respective user. In addition, you need to provide comfort and preferably should not require special efforts for cleaning and maintenance. These functions can be drastically improved when the superhydrophobic coating on said textiles is taken into account. By For example, when the outer part of an outer garment is provided with said superhydrophobic coating, the transpiration capacity is not reduced at the same time as the probability of rainwater entering the garment being drastically improved. This benefit is not only used on garments but also in accessories such as bathing suits, shoes and hats, as well as various materials such as fabrics or leather or synthetic materials. In addition, it can be used for articles that are designed to provide water repellency or impermeability particularly against rain. These textiles can be used for umbrellas, tents, blinds, protective canvas covers, awnings in cars or canopies. The coating according to the present invention does not alter the water vapor and (if present) air permeability of the textiles but reduces or even eliminates the possibility of liquid water passing through them. This is achieved by various means. First the hydrophobic coating as such reduces the contact surface between a drop of water and the textile due to the surface tension of the liquid. In addition, however, typically said textiles do not have absolute horizontal surfaces and use gravitational force to allow the liquid to flow. With the superhydrophobic coating according to the present invention this run is drastically accelerated so that the time in which a quantity of liquid can penetrate the textile is reduced. At the same time, these textiles will dry faster. Especially when they get wet, as, for example, in swimwear, the superhydrophobic coating will cause drying substantially faster 'and will even return the change of superfluous wet clothes. For example, children's swimsuits are usually removed to avoid kidney problems or long-term urinals or sand / dirt stickiness to the wet parts of the suit. In contrast, swimsuits that use superhydrophobic coating no longer require this change. In addition to the above benefits it is also worth mentioning that textiles permanently used on the outside with superhydrophobic coating have a reduced tendency to be soiled. When considering how dirt and stains are transported to textile surfaces it is clear that a reduction in the attraction between dirt and surface can provide a benefit, however, the accelerated run will also have a high probability of transporting dirt already deposited. outside of the garment. Finally, the liquid that remains on the surface normally contains a certain amount of solid material that after the evaporation of water remains on the textile surface. With an increased run probability of said liquids, the amount of waste deposited on the textile surface is also reduced with the superhydrophobic coating.

Claims (7)

NOVELTY OF THE INVENTION CLAIMS

1. - A textile article of which at least a part of the surface of said article is surface treated with a coating either inside a plasma reactor vessel, said container having a luminescent region and a post-luminescent region, or in a process Continuous passing through an energy emitter so that a direct exposure to the plasma in the luminescent region or to the energy emitter is achieved so that said coating provides a smooth and flat surface treated to have a contact angle with static water (WCA) of more of 120 °, preferably of more than 130 °, most preferably between 150 ° and approximately 165 °.

2. A textile article according to claim 1, further characterized in that said coating is a fluorocarbon coating.

3. A textile article according to claim 2, further characterized in that said coating exhibits a fluorine / carbon (F / C) ratio of between 1.50 and approximately 2.00, preferably between 1.60 and approximately 1.95.

4. A textile article according to any of the preceding claims, further characterized in that said article is permeable to water vapor. jj ^^ Jj

5. - A textile article according to claim 4,

6. - A textile article according to claims 1 to 3, further characterized in that said article is an automobile awning or a sun blind or canopy. - A textile article according to claim 1 3, further characterized in that said article is an article for swimming. REg FILM OF THE INVENTION & against the sun or canopies that have at least part of their surface provided with a superhydrophobic character, PG / tpr * osu * mmf P01 / 316F tekÜt? HI-i