WO2013011315A1 - Revêtements de surface - Google Patents

Revêtements de surface Download PDF

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Publication number
WO2013011315A1
WO2013011315A1 PCT/GB2012/051723 GB2012051723W WO2013011315A1 WO 2013011315 A1 WO2013011315 A1 WO 2013011315A1 GB 2012051723 W GB2012051723 W GB 2012051723W WO 2013011315 A1 WO2013011315 A1 WO 2013011315A1
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WO
WIPO (PCT)
Prior art keywords
cycle
pressure
monomer
formula
compound
Prior art date
Application number
PCT/GB2012/051723
Other languages
English (en)
Inventor
Stephen Richard Coulson
Paul DE BLAQUIERE
Delwyn EVANS
Warren Lee
Original Assignee
P2I Ltd
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 P2I Ltd filed Critical P2I Ltd
Priority to EP12753184.6A priority Critical patent/EP2734576A1/fr
Priority to CN201280045757.1A priority patent/CN103946286A/zh
Publication of WO2013011315A1 publication Critical patent/WO2013011315A1/fr
Priority to US14/511,784 priority patent/US20150065001A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/52—Polymerisation initiated by wave energy or particle radiation by electric discharge, e.g. voltolisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • 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
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/08—Organic compounds
    • D06M10/10—Macromolecular compounds
    • 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
    • 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
    • B05D2502/00—Acrylic polymers
    • 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
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/58—No clear coat specified
    • B05D7/586—No clear coat specified each layer being cured, at least partially, separately
    • 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
  • Such coatings typically include fluorocarbon chains, with the degree of oil and water repellency being a function of the number and length of fluorocarbon groups or moieties that can be fitted into the available space.
  • 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 monomer 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.
  • hydrocarbons and fluorocarbons hydrocarbons and fluorocarbons .
  • Residency time is the average amount of time that a particle spends in a particular system. Residency time can be defined by the equation
  • ⁇ C/Q [1] where ⁇ is residence time, C is the capacity of the processing chamber and Q is the flow rate of the gas through the system at the pressure in the chamber.
  • a first aspect of the present invention provides a method of forming a liquid repellent coating on a surface of a substrate, said method comprising exposing said surface to a monomer in a plasma deposition process under conditions that maintain the monomer in situ for a period of time to allow a polymeric layer to form on the surface, wherein the conditions comprise at least one cycle of varying pressure.
  • variable pressure cycling increases the residency time during which molecules of the monomer are prevalent in the processing chamber. This is due to the cycling keeping the pressure within the optimal range . It is desirable that the chamber remains within the optimal pressure range to maximise polymerisation .
  • variable pressure cycling improves the evenness of the coating, reduces the processing time and uses less monomer to produce a given thickness of coating.
  • the processing chamber may be provided with valve such as a gas exhaust gate, which is closed during introduction of the monomer.
  • the exhaust gate may be adjusted to open, closed or partially open.
  • the at least one cycle may comprise continually introducing the monomer into the processing chamber (for example by injection) and allowing the pressure to rise. Exhaust gas may be expelled from the processing chamber at the end of each cycle.
  • the processing chamber may be at least partly evacuated at the beginning of each cycle; this enables it to reach the low pressure optimal for the polymer coating to form.
  • waste gases such as water vapour can be vented without affecting the low pressure achieved at the beginning of the cycle.
  • the at least one cycle of varying pressure may comprise a time based cycle.
  • the processing chamber may be at least partly evacuated after a predetermined amount of time in each cycle. Time cycling is particularly beneficial in that it allows for the monomer to be retained in situ so increasing residency time which assists in improving the coating process.
  • the at least one cycle of varying pressure may comprise a pressure based cycle.
  • the processing chamber may be at least partly evacuated if the pressure falls outside the optimum range.
  • the processing chamber may comprise pressure sensors to determine the pressure within the chamber. Feedback from the pressure sensor may be used to adjust an exhaust gate of the processing chamber. For example, the exhaust gate may be closed if the pressure drops below the optimum range and the exhaust gate may be opened if the pressure rises above the optimum range.
  • a pressure based system is suitable for low outgassing products, such as hearing aids and mobile telephones, as it produces a long cycle within the desired pressure range.
  • pressure based cycles can be too short.
  • a time based cycle can be designed which allows the cycle to be of good length, gives the monomer a good residency time, whilst still staying near the optimal pressure.
  • variable pressure may be maintained below a maximum
  • the maximum pressure may be at or below 150 raTorr.
  • the maximum pressure may be at or below 125 raTorr .
  • Each cycle may be between 45 and 75 seconds. Each cycle may be approximately 60 seconds .
  • the method may comprise exposing the surface to two or more cycles of varying pressure and in particular up to four cycles. Said two or more cycles may comprise between 5 and 12 cycles. Alternatively, said two or more cycles may comprise 8 or 9 cycles .
  • the deposition process is a gas process.
  • the deposition process may be a plasma process, for example a plasma polymerisation process.
  • the coating may be applied using a pulsed plasma.
  • the liquid repellent coating may comprise an oil or water repellent coating.
  • the polymeric layer may be uniform. However, it may also be advantageous to form a non uniform polymeric layer, for example where the coating is used in a bio array.
  • the liquid repellent coating is suitable for surfaces on a wide range of substrates, for example fabric, metal, glass, ceramics, paper or polymer substrates. Items such as clothing (including footwear), laboratory consumables (including pipette tips), filtration membranes, electronic devices (including mobile phones, audio equipments, laptop computers and hearing aids), microfluidic devices and photovoltaic modules (such as solar panels) can all suitably be treated using the method of this invention .
  • Plasma polymers are typically generated by subjecting a coating forming precursor to an ionising electric field under low pressure conditions. Deposition occurs when excited species generated by the action of the electric field upon the precursor (radicals, ions, excited molecules etc) polymerise in the gas phase and react with the substrate surface to form a growing polymer film.
  • Suitable plasmas for use in the method described herein include non-equilibrium plasmas such as those generated by
  • radiofrequencies RF
  • microwaves microwaves or direct current (DC) .
  • DC direct current
  • RF radiofrequencies
  • Various forms of equipment may be used to generate gaseous plasmas. Generally these comprise containers or plasma chambers in which plasmas may be generated. Particular examples of such equipment are described for instance in WO2005/089961 and
  • the gas used within the plasma may comprise a vapour of the monomeric compound alone, but it may be combined with a carrier gas, in particular, an inert gas such as helium or argon.
  • a carrier gas in particular, an inert gas such as helium or argon.
  • helium is a preferred carrier gas as this can minimise fragmentation of the monomer.
  • the relative amount of the monomer vapour to carrier gas is suitably determined in accordance with procedures which are conventional in the art.
  • the amount of monomer added will depend to some extent on the nature of the particular monomer being used, the nature of the substrate being treated, the size of the plasma chamber etc.
  • monomer is delivered in an amount of from 50-600mg/min, for example at a rate of from 100- 150mg/min.
  • Carrier gas such as helium is suitably administered at a constant rate for example at a rate of from 5-90, for example from 15-30sccm.
  • the ratio of monomer to carrier gas will be in the range of from 100:1 to 1:100, for instance in the range of from 10:1 to 1:100, and in particular about 1:1 to 1:10. The precise ratio selected will be so as to ensure that the flow rate required by the process is achieved.
  • a preliminary continuous power plasma may be struck for example for from 0.5-10 minutes for instance for about 4 minutes, within the chamber.
  • This may act as a surface pre-treatment step, ensuring that the monomer attaches itself readily to the surface, so that as polymerisation occurs, the coating "grows" on the surface.
  • the pre-treatment step may be conducted before monomer is introduced into the chamber, in the presence of only the inert gas.
  • the plasma is then suitably switched to a pulsed plasma to allow polymerisation to proceed, at least when the monomer is present.
  • a glow discharge is suitably ignited by applying high frequency voltage, for example at 13.56MHz.
  • high frequency voltage for example at 13.56MHz.
  • electrodes which may be internal or external to the chamber, but in the case of the larger chamber are internal.
  • the gas, vapour or gas mixture is supplied at a rate of at least 1 standard cubic centimetre per minute (seem) and preferably in the range of from 1 to lOOsccm.
  • the monomer vapour this is suitably supplied at a rate of from 80-300mg/minute, for example at about 120mg per minute depending upon the nature of the monomer, whilst the pulsed voltage is applied.
  • Gases or vapours may be drawn or pumped into the plasma region.
  • gases or vapours may be drawn into the chamber as a result of a reduction in the pressure within the chamber, caused by use of an evacuating pump, or they may be pumped or injected into the chamber as is common in liquid handling.
  • Polymerisation is suitably effected using vapours of compounds of formula (I), which are kept within a pressure range of from 40 to 150mtorr, suitably at about 80-120mtorr.
  • the applied fields are suitably of power of from 0.2W to 20W, more suitably about 2W, applied as a pulsed field. These powers are suitable for use in a chamber having a volume of 50cm 3 . For larger or smaller chambers, a suitable power giving the same power density can be used.
  • the pulses are applied in a sequence which yields very low average powers, suitably at a duty cycle of up to 10% (i.e. an on:off ratio of up to 10% on) . More suitable, the duty cycle is from 0.1% to 1%.
  • the on pulses can be long or short.
  • the fields are suitably applied from 30 seconds to 90 minutes, preferably from 5 to 60 minutes, depending upon the nature of the compound of formula (I) and the item being treated etc.
  • a plasma chamber used is of sufficient volume to accommodate multiple items .
  • the plasma is created with a voltage as a pulsed field, at an average power of from 0.001 to 500w/m 3 , for example at from 0.001 to lOOw/m and suitably for the functional layer, at from 0.005 to 0.5 /m 3 .
  • These conditions are particularly suitable for depositing good quality uniform coatings, in large chambers, for example in chambers where the plasma zone has a volume of greater than 500cm 3 , for instance 0.5m 3 or more, such as from 0.5m 3 -10m 3 and suitably at about lm 3 .
  • the layers formed in this way have good mechanical strength.
  • the dimensions of the chamber will be selected so as to be selected so as to be selected so as to be selected.
  • elongate or rectangular chamber may be constructed or indeed cylindrical, or of any other suitable shape.
  • the chamber may be a sealable container, to allow for batch processes, or it may comprise inlets and outlets for the items, for example yarn, to allow it to be utilised in a continuous process.
  • the pressure may be a sealable container, to allow for batch processes, or it may comprise inlets and outlets for the items, for example yarn, to allow it to be utilised in a continuous process.
  • the pressure may be a sealable container, to allow for batch processes, or it may comprise inlets and outlets for the items, for example yarn, to allow it to be utilised in a continuous process.
  • the pressure for example yarn
  • the monomer may comprise a compound of formula (I)
  • R 1 , R 2 and R 3 are independently selected from hydrogen, alkyl, haloalkyl or aryl optionally substituted by halo; andR 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 (0) 0 (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 - (0) pR 6 (0) 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.
  • the monomers used are selected from monomers of formula (I) as defined above.
  • 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+ i where m is an integer of 1 or more, suitably from 1-20, and preferably from 4-12 such as 4, 6 or 8.
  • Suitable alkyl groups for R 1 , R 2 and R 3 have from 1 to 6 carbon atoms .
  • R 1 , R 2 and R 3 are hydrogen. In a particular embodiment R 1 , R 2 , R 3 are all hydrogen. In yet a further embodiment however R 3 is an alkyl group such as methyl or propyl .
  • Y-r 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 NN((RR 7 ))SS00 22 " wwhheerree RR 7 iiss hhyyddrrooggen or alkyl such as Ci_ 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 (0) 0 (CH 2 ) n R 5 (III) where n and R 5 as defined above in relation to formula (I) and R is hydrogen, Ci-io alkyl, or Ci_i 0 haloalkyl .
  • R 7 is hydrogen or Ci_ 6 alkyl such as methyl.
  • a particular example of a compound of formula (III) is a compound of formula (IV)
  • R is as defined above, and in particular is hydrogen and x is an integer of from 1 to 9, for instance from 4 to 9, and preferably 7.
  • the compound of formula (IV) is IH, IH, 2H, 2H-heptadecafluorodecylacrylate .
  • the compound of formula (IV) is a compound of formula (V)
  • a second aspect of the present invention provides a hydrophobic and/or oleophobic substrate which comprises a coating of a polymer which has been applied by the method.
  • the substrate may comprise, for example, a fabric or an item of clothing (including footwear) comprising said fabric.
  • the substrate may comprise an electronic device, microfluidic device, laboratory consumable or photovoltaic module .
  • any feature disclosed herein may be replaced by an alternative feature serving the same or a similar purpose.
  • FIG. 1 illustrates the apparatus for carrying out the
  • Figure 2 is a flow diagram showing the events within each variable pressure cycle.
  • a processing chamber 10 has a processing area 12 within it and an access door 14. Equipment for generating a plasma within the processing chamber are not shown .
  • a fluid input 16 is provided to allow monomer to be introduced into the chamber.
  • Other fluids may also be introduced via this fluid input, for example a carrier gas or a pre-treatment gas.
  • the processing chamber 10 is connected to a vacuum pump 18 via a gate valve 20.
  • the gate valve 20 can be closed or opened (either partially or fully) . When opened, the gate valve allows waste gases to be exhausted and when used in conjunction with the vacuum pump enables the pressure within the processing area reduced .
  • the apparatus also has a controller 22 which controls the fluid input, gate valve and vacuum pump.
  • the controller may be a microprocessor, PC or any other suitable device.
  • Figure 2 shows the sequence of events during a cycle.
  • the gate valve is opened and the vacuum pump partially evacuates the processing chamber.
  • the pressure in the processing chamber is brought down to a desired low pressure.
  • the low pressure allows for increased residency time of monomer (s) in the processing chamber as it/they cannot escape from the valve and flow downstream with the evacuated gases.
  • the gate valve is closed (or at least partially closed) and the fluid input is opened, this allows the monomer to be introduced into the chamber.
  • the pressure in the chamber gradually increases and in particular this is as a result of vaporisation of monomers introduced into the chamber.
  • the gate valve is opened so that the waste gases can be exhausted.
  • the controller controls the actions of the vacuum pump, gate valve and fluid input during these steps in each cycle.
  • the cycle is repeated to maintain the desired residency time of the monomer.
  • the cycling rate can be selected either by the time taken to reach a given pressure or by the duration that is needed to provide monomer conversion to polymer. A typical number of cycles that is used is four. Further the use of cycling allows for the deposition rate to be moved within the chamber so that there is more uniformity of coating. In particular the deposition is moved from the edges of the chamber to the centre to improve coating.
  • the cycles may be time based or pressure based.
  • the controller further includes a clock or counter which is used to control the length of each cycle and the timing of the events in each cycle.
  • each step occurs when the pressure within the processing area reaches a pre-determined value .
  • a hearing aid was coated using a monomer formula VI below.
  • the plasma polymerisation coating was applied in an inductively coupled glow discharge reactor with a leak rate of better than 6 x 10 ⁇ 9 mol s -1 and a monomer flow rate of 4mg/min or 3.2 mol s -1 .
  • This was connected to a two stage Edwards rotary pump via a liquid nitrogen cold trap, a thermocouple pressure gauge, and a monomer tube containing the monomer.
  • a 13.56 MHz radio frequency (RF) generator was used to power the electrical discharge.
  • a hearing aid having a textured ABS plastic exterior surface was placed into the centre of the chamber, which was then evacuated down to 20mTorr.
  • CW continuous wave
  • a pulsed wave (PW) was then applied at 450W at a duty cycle of 35 microseconds on and 10 milliseconds off (0.35%), whilst the monomer was injected into the chamber; 140 shots with 3 seconds between each shot .
  • the pressure within the chamber was cycled as follows: Once the chamber pressure reached 50mTorr, the gate valve was closed for 60 seconds. After 60 seconds has elapsed, the gate was opened by a fixed percentage (between 50 to 100%) . When pressure fell to 50mTorr, the gate was again closed for 60seconds and the cycle repeated. This was repeated for the duration of the PW cycle (i.e. approximately 420 seconds) .
  • a mobile telephone was coated, which included various substrates of plastic, glass and metal.
  • the same apparatus and monomer was used as described in example 1.
  • the chamber was evacuated to 20mTorr before igniting the glow discharge and subjecting the chamber to continuous wave (CW) of 150W for 30s, during which the monomer was injected into the chamber in two doses 3 seconds apart.
  • CW continuous wave
  • a pulsed wave (PW) was then applied at 300W at a duty cycle of 35 microseconds on and 10 milliseconds off (0.35%), whilst monomer was injected into the chamber; 140 shots with 3 seconds between each shot .
  • the pressure within the chamber was cycled as follows: Once the chamber pressure reached 50mTorr, the gate was closed for 60 seconds. After 60 seconds has elapsed, the gate was opened by a fixed percentage (between 50 to 100%) . When pressure fell to 50mTorr, the gate was gain closed for 60seconds and the cycle repeated. This was repeated for the duration of the PW cycle (i.e. approximately 420 seconds) .
  • the coating applied with pressure cycling results in a higher contact angle.
  • the contact angle changes very little following the abrasions. As before, this is believed to be due to the coating forming more quickly.
  • a mobile telephone was coated, which included various substrates of plastic, glass and metal.
  • the same apparatus and monomer was used as described in example 1.
  • the chamber was evacuated to 20mTorr before igniting the glow discharge and subjecting the chamber to continuous wave (CW) of 150W for 30s, during which the monomer was injected into the chamber in one dose.
  • CW continuous wave
  • a pulsed wave (PW) was then applied at 450W at a duty cycle of 35 microseconds on and 10 milliseconds off (0.35%), whilst monomer was injected into the chamber; 130 shots with 3 seconds between each shot .
  • PW pulsed wave
  • the pressure within the chamber was cycled by alternatively opening and closing the gate valve for periods of 60 seconds.
  • This method was repeated without the pressure cycling, during which the gate was left open for the duration of the CW and PW phases .
  • Table 3 shows greatly increased deposition on the inside of the telephone where pressure cycling is used, as compared to no cycling .
  • variable pressure cycling speeds up the process of achieving the performance levels desired, i.e. it speeds up the processing time.
  • the increase in residency time has additional advantages, for example improved penetration of the coatings into nooks and crannies, for example in electronic devices.
  • the increased residency time enables coatings to be formed from monomers which do not polymerise well in conventional conditions, for example shorter chain monomers such as lH,lH,2H,2H-tridecafluoro-octyl acrylate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Textile Engineering (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physical Vapour Deposition (AREA)
  • Chemical Vapour Deposition (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un procédé pour former un revêtement répulsif liquide sur une surface de substrat, ladite surface étant exposée à un monomère dans un processus de dépôt par plasma dans des conditions qui maintiennent le monomère in situ pendant une durée permettant la formation d'une couche polymère sur la surface, les conditions comprenant au moins un cycle de variation de pression.
PCT/GB2012/051723 2011-07-21 2012-07-19 Revêtements de surface WO2013011315A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP12753184.6A EP2734576A1 (fr) 2011-07-21 2012-07-19 Revêtements de surface
CN201280045757.1A CN103946286A (zh) 2011-07-21 2012-07-19 表面涂层
US14/511,784 US20150065001A1 (en) 2011-07-21 2014-10-10 Surface coatings

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1112516.8 2011-07-21
GBGB1112516.8A GB201112516D0 (en) 2011-07-21 2011-07-21 Surface coatings

Related Child Applications (2)

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US14233416 A-371-Of-International 2012-07-19
US14/511,784 Continuation US20150065001A1 (en) 2011-07-21 2014-10-10 Surface coatings

Publications (1)

Publication Number Publication Date
WO2013011315A1 true WO2013011315A1 (fr) 2013-01-24

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PCT/GB2012/051723 WO2013011315A1 (fr) 2011-07-21 2012-07-19 Revêtements de surface

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EP (1) EP2734576A1 (fr)
CN (1) CN103946286A (fr)
GB (2) GB201112516D0 (fr)
TW (1) TW201311365A (fr)
WO (1) WO2013011315A1 (fr)

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US8852693B2 (en) 2011-05-19 2014-10-07 Liquipel Ip Llc Coated electronic devices and associated methods
GB2528653A (en) * 2014-07-21 2016-02-03 P2I Ltd Novel sound product
CN107142465A (zh) * 2017-05-21 2017-09-08 无锡荣坚五金工具有限公司 一种循环小功率连续放电制备多功能性纳米防护涂层的方法
CN107142466A (zh) * 2017-05-21 2017-09-08 无锡荣坚五金工具有限公司 一种小功率连续放电制备多功能性纳米防护涂层的方法
CN107201510A (zh) * 2017-05-21 2017-09-26 无锡荣坚五金工具有限公司 一种周期交替放电制备多功能性纳米防护涂层的方法
CN107686986A (zh) * 2017-08-23 2018-02-13 江苏菲沃泰纳米科技有限公司 一种调制结构的有机硅纳米防护涂层的制备方法
US20180078000A1 (en) * 2014-10-16 2018-03-22 Europlasma Nv Method to Produce an Item of Footwear with Improved Wearing Comfort, and Item of Footwear Produced According to this Method
EP3569733A4 (fr) * 2017-01-23 2020-02-19 Jiangsu Favored Nanotechnology Co., Ltd Procédé de préparation d'un revêtement étanche à l'eau et résistant au claquage électrique

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CN110804358B (zh) * 2015-06-09 2021-09-17 P2I有限公司 涂层
CN108642955A (zh) * 2018-04-10 2018-10-12 西北师范大学 一种防水纸及其制备方法
US20230227689A1 (en) * 2020-05-18 2023-07-20 Jiangsu Favored Nanotechnology Co., LTD Water-resistant film layer and article thereof

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8852693B2 (en) 2011-05-19 2014-10-07 Liquipel Ip Llc Coated electronic devices and associated methods
GB2528653A (en) * 2014-07-21 2016-02-03 P2I Ltd Novel sound product
US20180078000A1 (en) * 2014-10-16 2018-03-22 Europlasma Nv Method to Produce an Item of Footwear with Improved Wearing Comfort, and Item of Footwear Produced According to this Method
EP3569733A4 (fr) * 2017-01-23 2020-02-19 Jiangsu Favored Nanotechnology Co., Ltd Procédé de préparation d'un revêtement étanche à l'eau et résistant au claquage électrique
CN107142465A (zh) * 2017-05-21 2017-09-08 无锡荣坚五金工具有限公司 一种循环小功率连续放电制备多功能性纳米防护涂层的方法
CN107142466A (zh) * 2017-05-21 2017-09-08 无锡荣坚五金工具有限公司 一种小功率连续放电制备多功能性纳米防护涂层的方法
CN107201510A (zh) * 2017-05-21 2017-09-26 无锡荣坚五金工具有限公司 一种周期交替放电制备多功能性纳米防护涂层的方法
CN107201510B (zh) * 2017-05-21 2018-09-21 江苏菲沃泰纳米科技有限公司 一种周期交替放电制备多功能性纳米防护涂层的方法
CN107686986A (zh) * 2017-08-23 2018-02-13 江苏菲沃泰纳米科技有限公司 一种调制结构的有机硅纳米防护涂层的制备方法
CN107686986B (zh) * 2017-08-23 2018-12-18 江苏菲沃泰纳米科技有限公司 一种调制结构的有机硅纳米防护涂层的制备方法

Also Published As

Publication number Publication date
CN103946286A (zh) 2014-07-23
GB2493264A (en) 2013-01-30
GB201112516D0 (en) 2011-08-31
TW201311365A (zh) 2013-03-16
EP2734576A1 (fr) 2014-05-28
GB201212808D0 (en) 2012-09-05

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