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EP1115903A1 - Substrats recouverts, extremement hydrophobes - Google Patents

Substrats recouverts, extremement hydrophobes

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Publication number
EP1115903A1
EP1115903A1 EP99968686A EP99968686A EP1115903A1 EP 1115903 A1 EP1115903 A1 EP 1115903A1 EP 99968686 A EP99968686 A EP 99968686A EP 99968686 A EP99968686 A EP 99968686A EP 1115903 A1 EP1115903 A1 EP 1115903A1
Authority
EP
European Patent Office
Prior art keywords
substrate
coating
substrates
wca
plasma
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99968686A
Other languages
German (de)
English (en)
Inventor
Riccardo D'agostino
Italo Corzani
Saswati Datta
Pietro Favia
Paul Amaat Raymond Gerard France
Ritalba Lamendola
Gianfranco Palumbo
Arseniy Valerevich Radomyselskiy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP99968686A priority Critical patent/EP1115903A1/fr
Publication of EP1115903A1 publication Critical patent/EP1115903A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/515—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using pulsed discharges

Definitions

  • the present invention relates to super hydrophobic coated substrates having a static water contact angle of more then 120°.
  • U.S. Pat. No. 3,498,527 teaches that paper board containers for liquids can be waterproofed by application of a waterproofing coating such as wax or polyethylene, and a similar method is shown in U.S. Pat. No. 2,708,645 for waterproofing paper drinking cups and in U.S. Pat. No. 3,212,697 for paper grocery sacks.
  • a waterproofing coating such as wax or polyethylene
  • temporary wet strength is imparted to paper by coating it with a polymeric alcohol-polymeric aldehyde reaction product.
  • a disposable sanitary napkin which consists of an adsorbent layer having a liquid-repellent backing of polyvinyl alcohol or similar material capable of initially repelling water but eventually solubilizing.
  • the degree of water-repellency therefore the lifetime of the napkin, is controlled by varying the thickness of the backing. Because the necessary life of the napkin cannot be predicted by manufacturer or user, the backing must be sufficiently thick to take account of all normal contingencies.
  • U.S. Pat. No. 3,542,028 is directed to a flushable sanitary napkin consisting of a cellulosic sheet treated with a fluoropolymer coating.
  • U.S. Pat. No. 3,559,650 teaches the preparation of a sanitary napkin having two flush-disposable sides separated by a waterproof film too thin to support itself once both faces of the napkin have disintegrated upon disposal.
  • Analogous to the process of coating a surface with a waterproofing substance is the concept of reacting a surface with another material so as to form a reaction product on the surface which has water-repellent properties.
  • U.S. Pat. Nos. 2,130,212 and 3,137,540 teach that materials such as polymeric alcohols may be reacted with other materials to increase their water-repellent properties.
  • the latter patent teaches treating polyvinyl alcohol articles with an aqueous emulsion of an aldehyde to impart water-repellency thereto.
  • U.S. Pat. No. 3,626,943 teaches that disposable diapers can be made from polyvinyl alcohol and waterproofed on one side by reaction with formaldehyde.
  • a known method of water and oil repellent finishing of textiles includes plasma treatment in a glow discharge in an atmosphere of inorganic gases, followed by treatment with a fluorine containing acrylic monomer in gas phase.
  • Another prior method of achieving film plasma polymerization described in U.S. Pat. No. 4,188,426, includes treatment in a glow discharge of per-fluoro-cyclo-butane or hexafluoroethane to reduce the friction coefficient and to improve the surface hydrophobia of organic and inorganic substrates (e.g. polyethylene films, metals).
  • organic and inorganic substrates e.g. polyethylene films, metals.
  • Plasma-deposited fluorocarbon coatings are often cited in the literature as "teflon-like coatings" because their CFx (0 ⁇ x ⁇ 2) composition and surface energy can be made very close to that of polytetrafluoroethylene (PTFE,-(CF 2 -CF 2 - ) 'I ), known on the market as Teflon®.
  • PTFE polytetrafluoroethylene
  • Plasma coating processes of metals, polymers, and other substrates, with fluoro- carbon films are known in the art.
  • deposition from continuous (i.e. non modulated) radiofrequency (RF) glow discharges fed with fluorocarbons provides films, layers, tapes, plates, and differently shaped articles made of plastics, metals or other materials, with a thin fluorocarbon coating, with no other material in- terposed between the coating itself and the substrate.
  • Such coatings are claimed to have very good adherence to the items processed, to be void-free, to be uniform or not porous, and to show controlled wettability characteristics, which depend on their surface chemical composition.
  • the non modulated, continuous plasma process of the above mentioned patent leads to coatings characterized by static water contact angle (WCA) values lower than 120°.
  • WCA static water contact angle
  • Glow discharges treatments are also considered in US-A-5 462 781 for improving the bondability of an implantable polymer medical device or for changing the wettability of a polymer fabric.
  • Several of the references discussed in this patent confirm non modulated, continuous plasma treatments as a means for varying the inherent WCA of a surface.
  • US-A-5 034 265 discloses a non modulated, continuous plasma treatment for improving the biocompatibility of vascular grafts with a CF ⁇ fluorocarbon coating deposited at the inside wall of the grafts in a proper plasma reactor fed with tetrafluoroethylene (C 2 F 4 , TFE) at 0.2 Torr.
  • C 2 F 4 , TFE tetrafluoroethylene
  • U.S. Pat No 5,328,576 discloses a method for imparting water and oil repellent surface properties to 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 glow discharge carried out in the same treatment chamber. This method doesn't deliver durable, permanent coatings with a WCA higher than about 120°.
  • U.S. Pat. No. 5,262,208 discloses an gas plasma treatment for archival preservation of paper manuscripts by a thin film protective polymer film.
  • the treatment time is ranging from 30-3600 seconds.
  • Other methods have been used to obtain thin coatings on the web materials with short treatment periods.
  • Providing surface treatment is disclosed in US Patent No. 4,842,893 and 4,954,371 which describe a process for high speed coating of substrates with a complete and uniformly adhering layer and using electron beam radiation curing of the vapor deposited monomers for multilayer capacitators.
  • U.S. Pat. No. 4,842,893 discloses high speed coating process including flash vaporization system and electron beam curing. Both of these electron beam disclosures are incorporated herein by reference.
  • Other uses of electron beam coatings in the electronic industry field have been reported by Westinghouse science & technology center USA (Adv. Mat. Newsletter Volume 13, No 9, 1991 page 4).
  • the present invention having the features mentioned in the annexed claims, relates to substrates coated with a thin, well adherent, nonporous, fluorocarbon coating with super hydrophobic properties, i.e. characterized by static water contact angle (WCA) values, measured on a smooth and plane surface, higher than about 120°, preferably higher than 130°, more preferably higher than 150°.
  • WCA static water contact angle
  • Substrates treated with this method have their hydrophobicity markedly improved, e.g. can be made effectively waterproof while maintaining their previous characteristics such as permeability to gases and vapors.
  • the increased hydrophobicity results also in additional benefits such as prevention of build-up of soiling (e.g.
  • the substrates are polymeric, they can be useful e.g. in making breathable products with improved resistance to leakage of body fluids.
  • the present invention deals with treated polymeric or non polymeric articles whose surface is made super hydrophobic, i.e. characterized by static water contact angle (WCA) values higher than about 120°, preferably higher than 130°, more preferably higher than 150°.
  • WCA static water contact angle
  • the substrates of interest for the present invention may include a wide range of materials in form of webs, tapes, films, powders, granules, particles, woven and non-woven layers; substrates can be porous or non-porous, molded or shaped, rigid or flexible, made of polymers, textiles, papers, cellulose derivatives, biodegradable materials, metals, ceramics, semiconductors, and other inorganic or organic materials.
  • the substrate is formed into a desired shape or configuration, depending on its intended use, before being subjected to the treatment object of this invention.
  • such substrate materials could be fabricated from polyethylene, polyacrylics, polypropylene, polyvinyl chloride, polyamides, polystyrene, polyurethanes, polyfluorocarbons, polyesters, silicone rubber, hydrocarbon rubbers, polycarbonates and other synthetic polymers.
  • the articles are preferably subjected to a modulated glow discharge plasma treatment performed with a fluorocarbon gas or vapor compound fed in a prop- erly configured reactor vessel where the substrates are positioned.
  • the plasma process deposits a continuous, fluorocarbon thin film with super hydrophobic surface characteristics, tightly bound to the substrate.
  • a more conventional thin film coating process followed by high energy surface curing can be used.
  • This is the method of using a high speed vacuum coating process for producing durable and thin water-repellent coatings on a substrate. It uses e.g. a movable support such as rotating drum in a vacuum chamber. The surface of the support is maintained at a temperature sufficient to permit condensation of a vaporized material deposited in the chamber.
  • the material is a curable monomer with a relatively low molecular weight.
  • the monomer vapor is created using a flash vaporizer.
  • the desired amount of curable monomer is metered to a heated flash vaporizer system where the material is vaporized. It is then transported e.g.
  • the substrate is then transported to a curing means such as an energy source which emits an electron beam, UV-light radiation or exposure to an electro magnetic field.
  • a curing means such as an energy source which emits an electron beam, UV-light radiation or exposure to an electro magnetic field.
  • the curable monomer can also be transferred into radicals by passing through a plasma zone (zone of high voltage discharge).
  • the curing of the monomer by the curing means then provides a coating on the substrate surface which has a static water contact angle of more than 95°.
  • the method for delivering the curable monomer to the substrate for minimizing the amount of monomers can use an ultrasonic atomizer producing micro droplets of curable monomer. They are released into a vaporization tube heated by band heaters. The atomized droplets impinge on the inner wall of the vaporization tube and are instantaneously vaporized, i.e., flash vaporized. This reduces the opportunity for polymerization prior to being deposited on the substrate.
  • the substrate can be one side water- repellent and capable of absorbing and storing fluids from the other side, 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 igniting a glow discharge in a low pressure gas through a power supply.
  • Glow discharges contain a variety of species chemically active and energetic enough to cause chemical reactions with surfaces exposed, i.e. covalent bonding to a suitable substrate material.
  • Cold plasmas, or glow dis- charges are generally produced with high frequency (from KHz to MHz and GHz) power supply (HF plasmas). Electrons, positive and negative ions, atoms, excited molecules, free radicals, and photons of various energies are formed in a cold plasma.
  • Modemated plasma means a non continuos plasma, HF plasma, i.e. a glow discharge whose driving power is pulsed between a maximum value and zero (ON/OFF pulse) or a fraction of it, at a certain frequency, with a proper pulse generator connected to the main power supply.
  • ON/OFF pulsed systems the time ON and time OFF values are among the experimental pa- rameters of the process.
  • superimposing a triggering ON/OFF pulse to the main high frequency field which generally drives a glow discharge alternates short continuous discharges with plasma OFF time intervals where active species still exists in the gas phase, but the effects of ions and electrons are strongly reduced. This alternating exposure to two different processes leads to unique sur- face modifications of substrates, which are very different from those of continuous plasma process, as it will be shown.
  • Plasma deposition or “plasma polymerization” is the plasma process that leads to the formation of thin (0.01 - 2 ⁇ m), partly crosslinked, void-free, continuous coatings well adherent to substrates.
  • the molecules of the gas phase are fragmented by energetic electrons, which are able to break chemical bonds; this process leads to radicals and other chemical species which are able to deposit at surfaces inside the vacuum chamber and form a thin, uniform film.
  • the action of the plasma may also affect the surface of a polymer substrate in the early deposition time; energetic species may break bonds in the substrate with possible evolution of gas products, such as hydrogen, and formation of free radical sites which contribute to form covalent bonds between the growing film and the substrate.
  • Substrate to be treated are subjected to modulated plasma gas discharge in the presence of at least one fluorocarbon gas or vapor.
  • fluorocarbon gases or vapors such as tetrafluoroethylene (TFE,C 2 F 4 ), hexafluoropropene (HFP,C 3 F 6 ), perfluoro-(2-trifluoromethyl-)pentene, perfluoro-(2-methylpent-2-ene) or its trimer may be used, TFE being the presently preferred choice.
  • the plasma deposition process is preferably performed by positioning the substrate in a properly arranged plasma reactor, connecting the reactor to a source of a fluoro- carbon gas or vapor, regulating flow and pressure of the gas inside the reactor, and sustaining a glow discharge in the reactor with a high frequency electric field in a pulsed (modulated) mode by means of a suitable pulsed power supply.
  • the parameters which define the glow discharge treatment includes the feed gas or vapor, its flow rate, its pressure, the position of the substrate inside the reactor, the design of the reactor, the exciting frequency of the power supply, the input power, the time ON and the time OFF of the pulsing system.
  • Substrates, as those listed in the abstract may be positioned in the "glow" region of the discharge, i.e. directly exposed to the plasma, or in the "afterglow” region, i.e. downstream respect to the visible glow. The two positions generally result in coatings with different composition and properties; treating the substrates with modulated glow discharge results also in different coatings respect to continuous treatments.
  • the present invention thus provides substrates of the type mentioned above, with fluorocarbon films characterized by a WCA value higher than 120°, preferably higher than 130°, more preferably higher than 150°.
  • fluorocarbon coatings with F/C ratio from about 1.50 to about 2.00 have been deposited, characterized by WCA values higher than about 120°, such as between about 155° and about 165°.
  • the coatings have been deposited at the surface of different polymer and non polymer substrates such as polyethylene (PE), polypropylene (PP) polyethyleneterephta- late (PET), and paper in form of films and fabrics, glass and silicon, among many.
  • PE polyethylene
  • PP polypropylene
  • PET polyethyleneterephta- late
  • the F/C ratio could be theoretically up to 3, if the coating would be formed only by a mono-molecular layer of CF 3 groups.
  • the thickness of the coatings depends on the duration of the plasma process at different conditions, and can be kept between 0.01 and 2 ⁇ m. It has been found that the nature of the substrate materials does not influence neither the chemical composition nor the thickness of the coatings. Coatings with WCA values up to about 165° (e.g. 165° ⁇ 5°)were obtained.
  • FIG. 2 portrays a typical scheme of a plasma reactor adapted for use within the context of the invention
  • - Figure 3 shows a C1 s ESCA signal of an uncoated polyethylene substrate wherein the signal is due only to C-H, C-C bonds of the substrate
  • - Figure 4 shows a C1s ESCA signal of a PE substrate coated with a fluorocarbon coating deposited as described in example 1 (glow position, continuous mode), with WCA of 100 ⁇ 5°; the signal is composed by components due to CF3, CF2, CF and CCF bonds of the fluorocarbon coating, and to C-H, C- C bonds due to surface contamination;
  • FIG. 5 shows a C1s ESCA signal of a PE substrate coated with a fluorocarbon coating deposited as described in example 1 (afterglow position, continuous mode), with WCA of 120 ⁇ 5°; the signal is composed by components due to CF3, CF2, CF and CCF bonds of the fluorocarbon coating, and to C-H, C- C bonds due to surface contamination; and
  • FIG. 6 shows a C1s ESCA signal of a PE substrate coated with a fluorocarbon coating deposited as described in example 1 (glow position, modulated mode), with WCA of 165 ⁇ 5°; the signal is composed by components due to CF3, CF2, CF and CCF bonds of the fluorocarbon coating, and to C-H, C-C bonds due to surface contamination.
  • Figure 1 compares a conventional "continuous" plasma (figure 1 a) with the modulated process of the invention, (figure 1 b) showing pulsed alternating plasma ON with plasma OFF (i.e. no plasma) times.
  • the two processes are schematized by referring to their driving signals.
  • the reactor 1 schematically shown in figure 2 was utilized not exclusively for de- veloping the deposition method object of the present invention.
  • the reactor vacuum chamber 1 is made of Pyrex glass, is provided with an external RF powered electrode 2 and an internal grounded electrode 3.
  • the external electrode is connected to a power supply 4 (typically a radiofrequency generator operating at e.g. 13.56 MHz) through a matching network and an ON/OFF pulse generator 5.
  • the substrates can be treated in the "glow” region of the reactor, onto the grounded electrode 3, as well as in its "afterglow” position i.e. at an afterglow substrate holder 6.
  • the gas/vapor is fed through a proper mass flowmeter through a gas/vapor feeding manifold 7, and its pressure, measured at the pump out exit 8 of the reactor, kept at a certain constant value with a manual valve on the vacuum connection between the reactor and its pumping unit.
  • the deposition process is performed with an RF (13.56 MHz) generator.
  • the RF power delivered to the external electrode of the reactor is kept in the 1-500 Watts range for a power density of 0.02-10 Watt/cm 2 .
  • the reactor is fed with a fluorocarbon compound at a 1-100 seem flow rate and is kept at a constant pressure of 50-1000 mTorr during the process.
  • the glow dis- charges are modulated through the pulse generator, preferably at 1-500 ms time ON and 1-1000 ms time OFF values, with respective values of about 10 ms and about 190 ms being the most preferred choice at present.
  • the deposition process may range from a few seconds to many hours; during this time a uniform fluorocarbon coating is deposited on the substrates positioned in the glow as well as on those in the afterglow region.
  • the deposition rate a typical one being in the 20 - 400 A/min range, was measured by weighing (weight/time) the substrates before and after the discharge, or by measuring the thickness of the coatings (thickness/time) with an Alpha Step profilometer.
  • the deposition rate and the chemical composition of the coating depend on the experimental condi- tions (pressure, power, substrate position time ON, time OFF, gas feed and flow rate) of the discharge.
  • the coatings obtained are uniform over the entire surface of the substrate; when deposited on flat (i.e. plane), smooth substrates, their hydrophobic character has been estimated through their static WCA value, as measured with a WCA goniometer.
  • the measurement is done on a flat, i.e. plane, and smooth surface of a substrate after coating.
  • the term smooth as used herein for water contact angle measurements refers to a roughness of no more than 5 microns in accordance with standard roughness measurements on continuous surfaces.
  • WCA values in the range about 120° to about 165°, corresponding to a critical surface tension lower than that of PTFE (18 dynes/cm) have been measured for fluorocarbon CFx coatings, when x ranges between about 1.50 and about 2.00.
  • the chemical composition of coatings is preferably determined by Electron Spectroscopy for Chemical Analysis (ESCA) within the sampling depth of the technique (about 100 A). The adherence of the coating to the substrate is very good.
  • the substrates were extracted from the reactor and their WCA measured.
  • the WCA values shown in Table 1 were found, which are compared to the WCA values of the unprocessed substrates.
  • a deposition rate of 30 ⁇ 5 A/min was measured for the coatings deposited in the modulated mode.
  • the substrates were extracted from the reactor and their WCA measured.
  • the WCA values shown in Table 3 were found, which are compared to the WCA values of the unprocessed substrates.
  • a deposition rate of 70 ⁇ 5 A/min was measured for the coatings deposited in the modulated mode.
  • the coated FAM substrate was cut along its thickness, and the freshly cut surface, which was not directly exposed to the discharge, analysed by WCA and ESCA measurements.
  • the data shown in Table 7 demonstrate that the thick FAM sample was treated not only on the surface exposed to the glow, but also inside its bulk, which demonstrates that the plasma treatment is able to penetrate through porous substrates.
  • 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 most preferably in the range of 0.001 to 1 microns.
  • the coatings are formed by depositing a vapor of curable monomer, under vacuum, on a movable substrate which is mounted in thermal contact with a support, for continuos processing preferably a rotating drum, which is maintained at a temperature below the boiling point of the vaporized monomer under the environmental conditions in vacuum chamber . As a result of this temperature differential, the monomer vapor condenses on the surface of the substrate.
  • the monomer materials utilized in the present invention are relatively low in molecular weight, between 150 and 1000 Atomic Mass Units (AMU) , and preferably in the range 200 to 300 AMU.
  • AMU Atomic Mass Unit
  • Polyfunctional flurocarbons and especially fluoroacrylates or mixtures of monofunctional fluoroacrylates and polyfunctional fluoroacrylates are preferred.
  • the monomers or monomer mixtures employed have an average of about two or more double bonds (i.e., a plurality of olefinic groups) and have a vapor pressure such that they condense on the substrate surface.
  • Such vapor pressures are for example pressure between about 1.33 10 ⁇ 6 mbar and 1.33 10 "1 mbar, most preferably a vapor pressure of approximately 1.33 10 "2 mbar at standard temperature and pressure, (i.e., relatively low boiling materials) are selected.
  • high-vapor-pressure monomers can be flash vaporized already at low temperatures and thus are not degraded (cracked) by the heating process.
  • the absence or low amount of unreactive degradation products results in coatings with a reduced levels of volatile components in which substantially all of the deposited monomer is reactive and will cure to form an integral film when exposed to a source of radiation.
  • 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 by organic solvents and inorganic salts.
  • the high speed vacuum coating process for producing water vapour permeable substrates with exceptional water repellent properties on either one side or both sides requires a curable monomer component.
  • the curable monomer for obtaining water-repellent coatings comprises fluoro-containing group.
  • any suitable fluoromonomer may be used, including, but not limited to, fluoroacrylate monomers, fluoro olefin monomers, fluorostyrene monomers, fluoroalkylene oxide monomers (e.g., perfluoropropylene oxide, perfluorocyclohexene oxide), fluorinated vinyl alkyl ether monomers, and the copolymers thereof with suitable comonomers, wherein the comonomers are fluorinated or unfluorinated. Fluoromonomers which are polymerized by a free radical polymerization process are preferred.
  • fluorostyrenes and fluorinated vinyl alkyl ether monomers which may be used in the method of the present invention include, but are not limited to, ⁇ -fluorostyrene; ⁇ -fluorostyrene; ⁇ , ⁇ -difluorostyrene; ⁇ , ⁇ - difluorostyrene; ⁇ , ⁇ , ⁇ -trifluorostyrene; ⁇ -trifluoromethylstyrene; 2,4,6-Tris (trifluoromethyl)styrene; 2,3,4,5,6-pentafluorostyrene; 2,3,4,5,6-pentafluoro- ⁇ - methylstyrene; and 2,3,4,5,6-pentafluoro- ⁇ -methylstyrene.
  • tetrafluoroethylene can also be used in the method of the present invention and include, but are not limited to, tetrafluoroethylene- hexafluoropropylene copolymers, tetrafluoroethylene-perfluorovinyl ether copolymers (e.g., copolymers of tetrafluoroethylene with perfluoropropyl vinyl ether), tetrafluoroethylene-ethylene copolymers, and perfluohnated ionomers (e.g., perfluorosulfonate ionomers; perfluorocarboxylate ionomers).
  • tetrafluoroethylene- hexafluoropropylene copolymers etrafluoroethylene-perfluorovinyl ether copolymers
  • tetrafluoroethylene-perfluorovinyl ether copolymers e.g., copolymers of tetrafluoroethylene with
  • fluorocarbon elastomers are a group of fluoro olefin polymers which 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 fluohde-co-hexafluoropropylene-co-tetrafluoroethylene); poly[vinylidene fluoride-co-tetrafluoroethylene-co-perfluoro(methyl vinyl ether)]; poly[tetrafluoroethylene-co-perfluoro(methyl vinyl ether)]; poly(tetrafluoroethylene-co-propylene; and poly(vinylidene fluoride-co- chlorotrifluoroethylene).
  • fluoroacrylates are particularly useful monomeric materials.
  • R 2 is a C, to C 8 perfluoroalkyl or - CH 2 - NR 3 - SO 2 - R 4 , wherein R 3 is C r C 2 alkyl and R 4 is C 1 to C 8 perfluoroalkyl.
  • perfluorinated means that all or essentially all hydrogen atoms on an organic group are replaced with fluorine.
  • Monomers illustrative of Formula (I) above, and their abbreviations, include the following: 2-(N-ethylperfluorooctanesulfonamido) ethyl acrylate (“EtFOSEA”); 2-(N-ethylperflooctanesulfonamido) ethyl methacrylate (“EtFOSEMA”); 2-(N-methylperfluorooctanesulfonamido) ethyl acrylate (“MeFOSEA”); 2-(N-methylperflooctanesulfonamido) ethyl methacrylate (“MeFOSEMA”); 1 ,1-Dihydroperfluorooctyl acrylate (“FOA”); and 1 ,1-Dihydroperfluorooctyl methacrylate (“FOMA”).
  • EtFOSEA 2-(N-ethylperfluorooct
  • the curable monomer component can also include polyfunctional acrylates, which are set forth in U.S. Patent 4,842,893.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Chemical Vapour Deposition (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

L'invention concerne un film mince continu de fluorocarbone, doté de caractéristiques de surface extrêmement hydrophobes, c'est-à-dire caractérisé par des valeurs statiques d'angle de contact avec l'eau, supérieures à environ 120°, de préférence supérieures à 130° et idéalement supérieures à 150°, ce film étant étroitement fixé sur un substrat.
EP99968686A 1998-09-07 1999-09-07 Substrats recouverts, extremement hydrophobes Withdrawn EP1115903A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99968686A EP1115903A1 (fr) 1998-09-07 1999-09-07 Substrats recouverts, extremement hydrophobes

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP98116894 1998-09-07
EP98116894A EP0985740A1 (fr) 1998-09-07 1998-09-07 Substrats revêtus super-hydrophobes
PCT/US1999/020503 WO2000014296A1 (fr) 1998-09-07 1999-09-07 Substrats recouverts, extremement hydrophobes
EP99968686A EP1115903A1 (fr) 1998-09-07 1999-09-07 Substrats recouverts, extremement hydrophobes

Publications (1)

Publication Number Publication Date
EP1115903A1 true EP1115903A1 (fr) 2001-07-18

Family

ID=8232589

Family Applications (2)

Application Number Title Priority Date Filing Date
EP98116894A Withdrawn EP0985740A1 (fr) 1998-09-07 1998-09-07 Substrats revêtus super-hydrophobes
EP99968686A Withdrawn EP1115903A1 (fr) 1998-09-07 1999-09-07 Substrats recouverts, extremement hydrophobes

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP98116894A Withdrawn EP0985740A1 (fr) 1998-09-07 1998-09-07 Substrats revêtus super-hydrophobes

Country Status (7)

Country Link
EP (2) EP0985740A1 (fr)
JP (1) JP2002524313A (fr)
CN (1) CN1146675C (fr)
AU (1) AU6028999A (fr)
BR (1) BR9913498A (fr)
CA (1) CA2342617A1 (fr)
WO (1) WO2000014296A1 (fr)

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US6635801B1 (en) 1999-05-14 2003-10-21 The Procter & Gamble Company Disposable absorbent article combining low viscosity liquid handling and high viscosity liquid handling
US6786894B2 (en) 1999-11-29 2004-09-07 The Procter & Gamble Company Absorbent article having liquid handling member which collapses under high pressures
EP1112728A1 (fr) 1999-12-23 2001-07-04 The Procter & Gamble Company Système de drainage de liquide qui assure une surface de contact plus séche
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EP1587862A1 (fr) 2003-01-30 2005-10-26 Europlasma Technique permettant d'enduire les surfaces d'un produit a l'aide d'un revetement a structure a alveoles ouvertes et applications de cette technique
US20060152817A1 (en) * 2005-01-12 2006-07-13 Goro Noto Optical device
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KR101194646B1 (ko) 2005-12-30 2012-10-24 엘지디스플레이 주식회사 소프트몰드 제조방법
WO2008063641A1 (fr) 2006-11-22 2008-05-29 The Procter & Gamble Company Compositions traitantes de textile et procédés correspondants
CN101985499A (zh) * 2010-10-28 2011-03-16 浙江工业大学 一种超疏水表面聚丙烯的制备方法
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KR101906574B1 (ko) * 2013-01-15 2018-10-10 주식회사 엘지생활건강 발수성을 가지는 칫솔모 및 이를 포함하는 칫솔
CN103590236B (zh) * 2013-10-24 2015-05-06 浙江理工大学 一种织物超疏水表面的制备方法
CN103898480A (zh) * 2014-03-25 2014-07-02 侯光辉 一种在电子装置上连续进行真空镀防水膜的装置及方法
ES2952839T3 (es) * 2016-04-14 2023-11-06 Sefar Ag Membrana de material compuesto y procedimiento para producir una membrana de material compuesto
ES2875608T3 (es) 2017-02-23 2021-11-10 Sefar Ag Medio de ventilación protector y procedimiento de producción de medio de ventilación protector
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CN108996915A (zh) * 2018-08-27 2018-12-14 深圳南科新材科技有限公司 一种疏水复合材料，其制备方法、用途和含有其的玻璃
CN109267038B (zh) * 2018-10-24 2019-12-06 江苏菲沃泰纳米科技有限公司 一种耐磨自交联的纳米涂层及其制备方法
CN110438475B (zh) * 2019-08-15 2022-02-15 佛山市思博睿科技有限公司 一种等离子化学气相沉积织物线材纳米疏水膜的制备方法
CN111321583A (zh) * 2020-02-18 2020-06-23 深圳奥拦科技有限责任公司 镀膜方法及镀膜件
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CN113413932B (zh) * 2021-06-29 2023-03-14 郑州大学 一种微流控芯片材料的疏水改性方法

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Also Published As

Publication number Publication date
CN1146675C (zh) 2004-04-21
JP2002524313A (ja) 2002-08-06
BR9913498A (pt) 2001-06-05
WO2000014296A1 (fr) 2000-03-16
CA2342617A1 (fr) 2000-03-16
AU6028999A (en) 2000-03-27
CN1317057A (zh) 2001-10-10
WO2000014296A9 (fr) 2000-06-15
EP0985740A1 (fr) 2000-03-15

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