EP2275598B1 - Revêtements de surface - Google Patents

Revêtements de surface Download PDF

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Publication number
EP2275598B1
EP2275598B1 EP10009211.3A EP10009211A EP2275598B1 EP 2275598 B1 EP2275598 B1 EP 2275598B1 EP 10009211 A EP10009211 A EP 10009211A EP 2275598 B1 EP2275598 B1 EP 2275598B1
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EP
European Patent Office
Prior art keywords
plasma
substrate
fabric
formula
compound
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.)
Expired - Lifetime
Application number
EP10009211.3A
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German (de)
English (en)
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EP2275598A1 (fr
Inventor
Jas Pal Singh Badyal
Stephen Richard Coulson
Colin Robert Willis
Stuart Anson Brewer
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P2i Ltd
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P2i Ltd
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Application filed by P2i Ltd filed Critical P2i Ltd
Priority claimed from EP19980928453 external-priority patent/EP0988412B1/fr
Publication of EP2275598A1 publication Critical patent/EP2275598A1/fr
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D06M14/20—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to the coating of surfaces, in particular to the production of oil- and water- repellent surfaces, as well as to coated articles obtained thereby.
  • Oil- and water- repellent treatments for a wide variety of surfaces are in widespread use. For example, it may be desirable to impart such properties to solid surfaces, such as metal, glass, ceramics, paper, polymers etc. in order to improve preservation properties, or to prevent or inhibit soiling.
  • a particular substrate which requires such coatings are fabrics, in particular for outdoor clothing applications, sportswear, leisurewear and in military applications. Their treatments generally require the incorporation of a fluoropolymer into or more particularly, fixed onto the surface of the clothing fabric.
  • the degree of oil and water repellency is a function of the number and length of fluorocarbon groups or moieties that can be fitted into the available space. The greater the concentration of such moieties, the greater the repellency of the finish.
  • Oil- and water-repellent textile treatments are generally based on fluoropolymers that are applied to fabric in the form of an aqueous emulsion.
  • the fabric remains breathable and permeable to air since the treatment simply coats the fibres with a very thin, liquid-repellent film.
  • cross-linking resins that bind the fluoropolymer treatment to fibres. Whilst good levels of durability towards laundering and dry-cleaning can be achieved in this way, the cross-linking resins can seriously damage cellulosic fibres and reduce the mechanical strength of the material.
  • Plasma deposition techniques have been quite widely used for the deposition of polymeric coatings onto a range of surfaces. This technique is recognised as being a clean, dry technique that generates little waste compared to conventional wet chemical methods. Using this method, plasmas are generated from small organic molecules, which are subjected to an ionising electrical field under low pressure conditions. When this is done in the presence of a substrate, the ions, radicals and excited molecules of the compound in the plasma polymerise in the gas phase and react with a growing polymer film on the substrate. Conventional polymer synthesis tends to produce structures containing repeat units which bear a strong resemblance to the monomer species, whereas a polymer network generated using a plasma can be extremely complex.
  • US Patent No 5,328,576 describes the treatment of fabric or paper surfaces to impart liquid repellent properties by subjecting the surfaces to a pre-treatment with an oxygen plasma, followed by plasma polymerisation of methane.
  • Japanese application no. 816773 describes the plasma polymerisation of compounds including fluorosubstituted acrylates. In that process, a mixture of the fluorosubstituted acrylate compounds and an inert gas are subjected to a glow discharge.
  • US 5 041 304 discloses plasma polymerisation of partially fluorinated alkenes and perfluorinated alkenes and cycloalkanes at atmospheric pressure by glow discharge of a gas mixture containing an inert gas.
  • the compounds mentioned include, for example, fluoropropylene, difluoropropylene etc, difluorobutene, trifluorobutene etc, but perfluorinated compounds such as hexafluoropropylene and octafluorocyclobutane are preferred.
  • the applicants have found an improved method of producing halopolymer coatings which are water and/or oil repellent on surfaces.
  • n is an integer of from 1 to 10 and R 5 is a C6-20 perhaloalkyl group.
  • halo or halogen refers to fluorine, chlorine, bromine and iodine. Particularly preferred halo groups are fluoro.
  • R 5 is a perfluoroalkyl group of formula C m F 2m+1 where m is an integer from 6 to 12, such as 8 or 10.
  • hydrocarbon includes to alkyl, alkenyl or aryl groups.
  • aryl refers to aromatic cyclic groups such as phenyl or napthyl, in particular phenyl.
  • alkyl refers to straight or branched chains of carbon atoms, suitably of up to 20 carbon atoms in length.
  • alkenyl refers to straight or branched unsaturated chains suitably having from 2 to 20 carbon atoms.
  • Monomeric compounds where the chains comprise unsubstituted alkyl or alkenyl groups are suitable for producing coatings which are water repellent. By substituting at least some of the hydrogen atoms in these chains with at least some halogen atoms, oil repellency may also be conferred by the coating.
  • Suitable plasmas for use in the method of the invention include non-equilibrium plasmas such as those generated by radiofrequencies (Rf), microwaves or direct current (DC). They may operate at atmospheric or sub-atmospheric pressures as are known in the art.
  • Rf radiofrequencies
  • DC direct current
  • the plasma may comprise the monomeric compound alone, in the absence of other gases or in mixture with for example an inert gas.
  • Plasmas consisting of monomeric compound alone may be achieved as illustrated hereinafter, by first evacuating the reactor vessel as far as possible, and then purging the reactor vessel with the organic compound for a period sufficient to ensure that the vessel is substantially free of other gases.
  • the surface coated in accordance with the invention may be of any solid substrate, such as fabric, metal, glass, ceramics, paper or polymers.
  • the surface comprises a fabric substrate such as a cellulosic fabric, to which oil- and/or water-repellency is to be applied.
  • the fabric may be a synthetic fabric such as an acrylic/nylon fabric.
  • the fabric may be untreated or it may have been subjected to earlier treatments.
  • treatment in accordance with the invention can enhance the water repellency and confer a good oil-repellent finish onto fabric which already has a silicone finish which is water repellent only.
  • Preciese conditions under which the plasma polymerization takes place in an effective manner will vary depending upon factors such as the nature of the polymer, the substrate etc. and will be determined using routine methods and/or the techniques illustrated hereafter.
  • polymerisation is suitably effected using vapours of compounds, of formula (I) at pressures of from 0.01 to 10 mbar, suitably at about 0.2mbar.
  • a glow discharge is then ignited by applying a high frequency voltage, for example at 13.56MHz.
  • Suitable conditions include continuous fields.
  • the pulses are applied in a sequence which yields very low average powers, for example of less than 10W and preferably of less than 1W. Examples of such sequences are those in which the power is on for 20 ⁇ s and off for from 10000 ⁇ s to 20000 ⁇ s.
  • the fields are suitably applied for a period sufficient to give the desired coating. In general this will be from 30 seconds to 20 minutes, preferably from 2 to 15 minutes, depending upon the nature of the compound of formula (I) and the substrate etc.
  • Plasma polymerisation of compounds of formula (I), particularly at low average powers has been found to result in the deposition of highly fluorinated coatings which exhibit super-hydrophobicity.
  • a high level of structural retention of the compound of formula (I) occurs in the coating layer, which may be attributed to the direct polymerisation of the alkene monomer via its highly susceptible double bond.
  • the process of the invention may have oleophobic as well as hydrophobic surface properties.
  • the invention further provides a hydrophobic or oleophobic substrate which comprises a substrate comprising a coating of a haloalkyl polymer which has been applied by the method described above.
  • the substrates are fabrics but they may be solid materials such as biomedical devices.
  • thermocouple pressure gauge (6) was connected by way of a Young's tap (7) to the reactor vessel (2).
  • An L-C matching unit (11) and a power meter (12) was used to couple the output of a 13.56 MHz R.F. generator (13), which was connected to a power supply (14), to copper coils (15) surrounding the reactor vessel (2).
  • This arrangement ensured that the standing wave ratio (SWR) of the transmitted power to partially ionised gas in the reactor vessel (2) could be minimised.
  • a pulsed signal generator (16) was used to trigger the R.F. power supply, and a cathode ray oscilloscope (17) was used to monitor the pulse width and amplitude.
  • ⁇ P > P CW T on / T on + T off where T on /(T on + T off ) is defined as the duty cycle and P CW is the average continuous wave power.
  • the reactor vessel (2) was cleaned by soaking overnight in a chloros bleach bath, then scrubbing with detergent and finally rinsing with isopropyl alcohol followed by oven drying. The reactor vessel (2) was then incorporated into the assembly shown in Figure 1 and further cleaned with a 50W air plasma for 30 minutes. Next the reactor (2) vessel was vented to air and the substrate to be coated (19), in this case a glass slide, was placed in the centre of the chamber defined by the reactor vessel (2) on a glass plate (18). The chamber was then evacuated back down to base pressure (7.2 x 10 -3 mbar).
  • Perfluoroalkene vapour was then introduced into the reaction chamber at a constant pressure of ⁇ 0.2 mbar and allowed to purge the plasma reactor, followed by ignition of the glow discharge. Typically 2-15 minutes deposition time was found to be sufficient to give complete coverage of the substrate. After this, the R.F. generator was switched off and the perfluoroalkene vapour allowed to continue to pass over the substrate for a further 5 minutes before evacuating the reactor back down to base pressure, and finally venting up to atmospheric pressure.
  • the deposited plasma polymer coatings were characterised immediately after deposition by X-ray photoelectron spectroscopy (XPS). Complete plasma polymer coverage was confirmed by the absence of any Si (2p) XPS signals showing through from the underlying glass substrate.
  • XPS X-ray photoelectron spectroscopy
  • C F 2 and C F 3 groups are the prominent environments in the C(1s) XPS envelope:- C F 2 (291.2 eV) 61% C F 3 (293.3 eV) 12%

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Materials For Medical Uses (AREA)
  • Wrappers (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Organic Insulating Materials (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Polishing Bodies And Polishing Tools (AREA)

Claims (6)

  1. Méthode de revêtement d'une surface avec une couche de polymère repoussant l'huile et l'eau, laquelle méthode comprend l'exposition de ladite surface à un champ de plasma à ondes continues comprenant le composé de formule (I)

            CH2 = CHC(O)O(CH2)nR5     (I)

    dans laquelle la puissance moyenne du champ est inférieure à 1 W, n est un nombre entier de 1 à 10 et R5 est un groupe perhalogénoalkyle en C6-C20.
  2. Méthode selon la revendication 1, dans laquelle R5 est un groupe perfluoroalkyle de formule CmF2m+1, où m est un nombre entier de 6 à 12.
  3. Méthode selon la revendication 1 ou la revendication 2, dans laquelle la surface est une surface d'un substrat en tissu, en métal, en verre, en céramique, en papier ou en polymère.
  4. Méthode selon la revendication 3, dans laquelle le substrat est un tissu.
  5. Méthode selon une quelconque revendication précédente, dans laquelle le traitement au plasma est fourni par une décharge luminescente allumée dans une atmosphère contenant le composé à une pression gazeuse de 0,01 à 10 mbar par une tension à haute fréquence.
  6. Méthode selon une quelconque revendication précédente, dans laquelle la polymérisation au plasma a lieu pendant 2 à 15 minutes.
EP10009211.3A 1997-06-14 1998-06-11 Revêtements de surface Expired - Lifetime EP2275598B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9712338.4A GB9712338D0 (en) 1997-06-14 1997-06-14 Surface coatings
EP19980928453 EP0988412B1 (fr) 1997-06-14 1998-06-11 Revetements de surface
EP05007277A EP1557489B1 (fr) 1997-06-14 1998-06-11 Revetements de surface

Related Parent Applications (4)

Application Number Title Priority Date Filing Date
EP05007277A Division EP1557489B1 (fr) 1997-06-14 1998-06-11 Revetements de surface
EP19980928453 Division EP0988412B1 (fr) 1997-06-14 1998-06-11 Revetements de surface
EP98928453.4 Division 1998-06-11
EP05007277.6 Division 2005-04-04

Publications (2)

Publication Number Publication Date
EP2275598A1 EP2275598A1 (fr) 2011-01-19
EP2275598B1 true EP2275598B1 (fr) 2014-12-17

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ID=10814111

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EP10009211.3A Expired - Lifetime EP2275598B1 (fr) 1997-06-14 1998-06-11 Revêtements de surface
EP05007277A Expired - Lifetime EP1557489B1 (fr) 1997-06-14 1998-06-11 Revetements de surface

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EP05007277A Expired - Lifetime EP1557489B1 (fr) 1997-06-14 1998-06-11 Revetements de surface

Country Status (8)

Country Link
US (1) USRE43651E1 (fr)
EP (2) EP2275598B1 (fr)
AT (1) ATE500377T1 (fr)
DE (1) DE69842159D1 (fr)
DK (2) DK2275598T3 (fr)
ES (2) ES2357957T3 (fr)
GB (2) GB9712338D0 (fr)
PT (2) PT1557489E (fr)

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AU744202B2 (en) 1997-08-08 2002-02-21 Board Of Regents Non-fouling, wettable coated devices
WO2000055260A1 (fr) 1999-03-18 2000-09-21 International Coatings Ltd. Composition de revetement pour substrats metalliques
MXPA03002988A (es) 2000-10-04 2004-12-06 Dow Corning Ireland Ltd Metodo y aparato para formar un recubrimiento.
EP1390421A1 (fr) 2001-05-23 2004-02-25 NKT Research & Innovation A/S Procede de polymerisation de plasma de benzenes substitues, materiau polymere pouvant etre obtenu par ledit procede, et utilisation dudit materiau
WO2003090939A1 (fr) 2002-04-25 2003-11-06 Nkt Research & Innovation A/S Procede et appareil de depot par projection plasma de groupes chimiquement reactifs sur des substrats, substrats chimiquement reactifs obtenus par la mise en oeuvre dudit procede, et utilisation desdits substrats
WO2004088710A2 (fr) 2003-04-02 2004-10-14 Nkt Research & Innovation A/S Procede et appareil de traitement au plasma gazeux a longueur controlee de plasma gazeux et utilisation correspondante
GB0406049D0 (en) 2004-03-18 2004-04-21 Secr Defence Surface coatings

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DE69842159D1 (de) 2011-04-14
ATE500377T1 (de) 2011-03-15
PT1557489E (pt) 2011-04-06
PT2275598E (pt) 2015-02-06
DK2275598T3 (da) 2015-02-09
ES2357957T3 (es) 2011-05-04
DK1557489T3 (da) 2011-04-18
EP1557489A1 (fr) 2005-07-27
GB9720078D0 (en) 1997-11-19
EP1557489B1 (fr) 2011-03-02
USRE43651E1 (en) 2012-09-11
ES2530418T3 (es) 2015-03-02
GB9712338D0 (en) 1997-08-13
EP2275598A1 (fr) 2011-01-19

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