USRE43651E1 - Surface coatings - Google Patents

Surface coatings Download PDF

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USRE43651E1
USRE43651E1 US11/113,340 US11334000A USRE43651E US RE43651 E1 USRE43651 E1 US RE43651E1 US 11334000 A US11334000 A US 11334000A US RE43651 E USRE43651 E US RE43651E
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group
formula
coating
compound
integer
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Jas P. S. Badyal
Stephen Richard Coulson
Colin R. Willis
Stuart A. Brewer
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P2i Ltd
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UK Secretary of State for Defence
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Priority claimed from US09/445,800 external-priority patent/US6551950B1/en
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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 hind 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.
  • U.S. Pat. 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.
  • the applicants have found an improved method of producing polymer and particular halopolymer coatings which are water and/or oil repellent on surfaces.
  • a method of coating a surface with a polymer layer comprises exposing said surface to a plasma comprising a monomeric unsaturated organic compound which comprises an optionally substituted hydrocarbon group, wherein the optional substituents are halogen; provided that where the compound is a straight chain perhalogenated alkene, it includes at least 5 carbon atoms; so as to form an oil or water repellent coating on said substrate.
  • Unsaturated organic compounds are those which contain at least one double bond which is capable of reacting to form a polymeric compound.
  • the compounds used in the method of the invention suitably include at least one optionally substituted hydrocarbon chain. Suitable chains, which may be straight or branched, have from 3 to 20 carbon atoms, more suitably from 6 to 12 carbon atoms
  • Monomeric compounds used in the method may include the double bond within a chain and so comprise alkenyl compounds.
  • the compounds may comprise an alkyl chain, optionally substituted by halogen, as a substitutent which is attached to an unsaturated moiety either directly or by way of an functional group, such as a ester or sulphonamide group.
  • halo or “halogen” refers to fluorine, chlorine, bromine and iodine. Particularly preferred halo groups are fluoro.
  • 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.
  • the monomeric compounds include haloalkyl moieties or comprise haloalkenyls. Therefore, preferably the plasma used in the method of the invention will comprise a monomeric unsaturated haloalkyl containing organic compound.
  • 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.
  • Particularly suitable monomeric organic compounds are those of formula (I)
  • R 1 , R 2 and R 3 are independently selected from hydrogen, alkyl, haloalkyl or aryl optionally substituted by halo; and R 4 is a group X—R 5 where R 5 is an alkyl or haloalkyl group and X is a bond; a group of formula —C(O)O(CH 2 ) n Y— where n is an integer of from 1 to 10 and Y is a bond or a sulphonamide group; or a group —(O) p R 6 (O) q (CH 2 ) t — where R 6 is aryl optionally substituted by halo, p is 0 or 1, q is 0 or 1 and t is 0 or an integer of from 1 to 10, provided that where q is 1, t is other than 0.
  • Suitable haloalkyl groups for R 1 , R 2 , R 3 and R 5 are fluoroalkyl groups.
  • the alkyl chains may be straight or branched and may include cyclic moieties.
  • the alkyl chains suitably comprise 2 or more carbon atoms, suitably from 2-20 carbon atoms and preferably from 6 to 12 carbon atoms.
  • alkyl chains are generally preferred to have from 1 to 6 carbon atoms.
  • R 5 is a haloalkyl, and more preferably a perhaloalkyl group, particularly a perfluoroalkyl group of formula C m F 2m+1 where m is an integer of 1 or more, suitably from 1-20, and preferably from 6-12 such as 8 or 10.
  • Suitable alkyl groups for R 1 , R 2 and R 3 have from 1 to 6 carbon atoms.
  • At least one of R 1 , R 2 and R 3 is hydrogen and preferably R 1 , R 2 , R 3 are all hydrogen.
  • n is an integer which provides a suitable spacer group.
  • n is from 1 to 5, preferably about 2.
  • Suitable sulphonamide groups for Y include those of formula —N(R 7 )SO 2 where R 7 is hydrogen or alkyl such as C 1-4 alkyl, in particular methyl or ethyl.
  • the compound of formula (I) is a compound of formula (II) CH 2 ⁇ CH—R 5 (II) where R 5 is as defined above in relation to formula (I).
  • the compound of formula (I) is an acrylate of formula (III) CH 2 ⁇ CR 7 C(O)O(CH 2 ) n R 5 where n and R 5 as defined above in relation to formula (I) and R 7 is hydrogen or C 1-6 alkyl, such as methyl.
  • 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.
  • polymerisation is suitably effected using vapours of compounds of formula (I) at pressures of from 0.01 to 10 mbar, suitably at about 0.2 mbar.
  • a glow discharge is then ignited by applying a high frequency voltage, for example at 13.56 MHz.
  • the applied fields are suitably of average power of up to 50 W. Suitable conditions include pulsed or continuous fields, but are preferably pulsed fields.
  • the pulses are applied in a sequence which yields very low average powers, for example of less than 10 W and preferably of less than 1 W. 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 for instance a fluoroalkene monomer via its highly susceptible double bond.
  • a surface is exposing a surface to a plasma comprising a compound of formula (III) as defined above, wherein the plasma being created by a pulsed voltage also as described above.
  • 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 alkyl polymer and particularly 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.
  • FIG. 1 shows a diagram of the apparatus used to effect plasma deposition
  • FIG. 2 is a graph showing the characteristics of continuous wave plasma polymerisation of 1H, 1H, 2H-pefluoro-1-dodecene;
  • FIG. 4 is a graph showing the characteristics of (a) continuous and (b) pulsed plasma polymerisation of 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate.
  • thermocouple pressure gauge ( 6 ) was connected by way of a Young's tap ( 7 ) to the reactor vessel ( 2 ).
  • a further Young's tap ( 8 ) connected with an air supply and a third ( 9 ) lead to an E2M2 two stage Edwards rotary pump (not shown) by way of a liquid nitrogen cold trap ( 10 ). All connections were grease free.
  • 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.
  • 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 as shown in FIG. 1 and further cleaned with a 50 W 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 ⁇ 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
  • FIG. 3 shows the C (1s) XPS spectrum for a 5 minute pulsed plasma polymerisation experiment
  • CF 2 region is better resolved and has greater intensity which means less fragmentation of the perfluoroalkyl tail compared to continuous wave plasma polymerisation.
  • the water repellency tests comprises placing 3 drops of a standard test liquid consisting of specified proportions of water and isopropyl alcohol by volume onto the plasma polymerised surface. The surface is considered to repel this liquid if after 10 seconds, 2 of the 3 drops do not wet the fabric. From this, the water repellency rating is taken as being the test liquid with the greater proportion of isopropyl alcohol which passes the test.
  • the oil repellency test 3 drops of hydrocarbon liquid are placed on the coated surface. If after 30 seconds no penetration or wetting of the fabric at the liquid-fabric interface occurs around 2 of the 3 drops is evident, then the test is passed.
  • the oil repellency rating is taken to be the highest-numbered test liquid which does not wet the fabric surface (where the increasing number corresponds to decreasing hydrocarbon chain and surface tension).
  • Example 1 The method of Example 1 described above was repeated using 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate (Fluorochem F04389E, 98% purity) in place of the perfluoroalkene.
  • low average powers were used for continuous wave and pulsed plasma polymerisation experiments.
  • FIG. 4(a) the XPS spectrum of a 1 W continuous wave plasma polymer deposited onto a glass slide for 10 minutes is shown in FIG. 4(a) .
  • FIG. 4(b) shows the C(1s) XPS spectrum for a 10 minutes pulsed plasma polymerisation experiment where
  • Table 3 compares the theoretical (taken from the monomer, CH 2 ⁇ CHCO 2 CH 2 CH 2 C 8 F 17 ) environments with what is actually found for polymer coatings.
  • the CF 2 group is the prominent environment in the C(1s) XPS envelope at 291.2 eV.
  • the remaining carbon environments being CF 3 , partially fluorinated and oxygenated carbon centres and a small amount of hydrocarbon (C x H y ).
  • the chemical composition of the coatings deposited for continuous wave and pulsed plasma conditions are given below in Table 4 (excluding satellite percentages) along with the theoretically expected compositions).
  • these coatings are highly hydrophobic and oleophobic and the coatings have good durability.
  • a sample of the same material was subjected to a two stage deposition process in which the fabric was first exposed to a continuous wave 30 W air plasma for 5 seconds followed by exposure to the same acrylate vapour only. The products were then tested for oil and water repellency as described in Example 2.
  • the process of the invention can not only enhance the water repellency of such as fabric, and also confer oil repellency, the durability of the coating is higher than that obtained using the known two step grafting polymerisation process.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials For Medical Uses (AREA)
  • Organic Insulating Materials (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Wrappers (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
US11/113,340 1997-06-14 1998-06-11 Surface coatings Expired - Lifetime USRE43651E1 (en)

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GBGB9712338.4A GB9712338D0 (en) 1997-06-14 1997-06-14 Surface coatings
GB9712338 1997-06-14
GB9720078 1997-09-23
GBGB9720078.6A GB9720078D0 (en) 1997-06-14 1997-09-23 Surface coatings
US11/113,340 USRE43651E1 (en) 1997-06-14 1998-06-11 Surface coatings
US09/445,800 US6551950B1 (en) 1997-06-14 1998-06-11 Surface coatings
PCT/GB1998/001702 WO1998058117A1 (en) 1997-06-14 1998-06-11 Surface coatings

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EP (2) EP2275598B1 (da)
AT (1) ATE500377T1 (da)
DE (1) DE69842159D1 (da)
DK (2) DK2275598T3 (da)
ES (2) ES2357957T3 (da)
GB (2) GB9712338D0 (da)
PT (2) PT2275598E (da)

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US20060008592A1 (en) * 2002-03-23 2006-01-12 University Of Durham Preparation of superabsorbent materials by plasma modification
US20100285301A1 (en) * 2007-11-09 2010-11-11 Dieudonne Marie Breathable Membranes and Method for Making Same
US8852693B2 (en) 2011-05-19 2014-10-07 Liquipel Ip Llc Coated electronic devices and associated methods
US9668355B2 (en) 2013-03-15 2017-05-30 Hzo Inc. Combining different types of moisture-resistant materials
US9795989B2 (en) 2013-03-15 2017-10-24 Hzo, Inc. Combining different types of moisture-resistant materials
US10328460B2 (en) 2014-02-28 2019-06-25 P2I Ltd Coating
US10421876B2 (en) * 2015-06-09 2019-09-24 P2I Ltd Coatings
US10428455B2 (en) 2013-12-13 2019-10-01 The North Face Apparel Corp. Plasma treatments for coloration of textiles, fibers and other substrates

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GB2434369B (en) 2006-01-20 2010-08-25 P2I Ltd Plasma coated electrical or electronic devices
GB2434368B (en) 2006-01-20 2010-08-25 P2I Ltd Plasma coated laboratory consumables
DE102006060932A1 (de) * 2006-12-20 2008-07-03 Carl Freudenberg Kg Temperaturstabile plasmabehandelte Gebilde und Verfahren zu deren Herstellung
GB2451176A (en) * 2007-07-17 2009-01-21 P2I Ltd Plasma coating
GB0721202D0 (en) * 2007-10-30 2007-12-05 P2I Ltd Novel method
GB2454242A (en) * 2007-11-02 2009-05-06 P2I Ltd Plasma coating
GB2475685A (en) * 2009-11-25 2011-06-01 P2I Ltd Plasma polymerization for coating wool
US8551895B2 (en) 2010-12-22 2013-10-08 Kimberly-Clark Worldwide, Inc. Nonwoven webs having improved barrier properties
EP2589438B1 (en) 2011-11-07 2017-05-03 Vlaamse Instelling voor Technologisch Onderzoek (VITO) Plasma surface activation method and resulting object

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