EP2279801B1 - Procédés de revêtement utilisant un jet de plasma et appareil de revêtement au plasma - Google Patents

Procédés de revêtement utilisant un jet de plasma et appareil de revêtement au plasma Download PDF

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Publication number
EP2279801B1
EP2279801B1 EP09166450.8A EP09166450A EP2279801B1 EP 2279801 B1 EP2279801 B1 EP 2279801B1 EP 09166450 A EP09166450 A EP 09166450A EP 2279801 B1 EP2279801 B1 EP 2279801B1
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Prior art keywords
plasma
nozzle
polymers
inorganic
organic
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German (de)
English (en)
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EP2279801A1 (fr
Inventor
Dr. Uwe Lommatzsch
Dr. Sabine Amberg-Schwab
Dipl.-Ing. Ulrike Weber
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • 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
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/126—Detonation spraying
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating

Definitions

  • the present invention relates to methods for coating substrates with inorganic-organic hybrid polymer material, as well as to a plasma coating apparatus suitable for use in the methods.
  • Substrates, such as plastic substrates, coated with the inorganic-organic hybrid polymer material according to the coating methods of the invention have excellent surface properties, in particular barrier properties against oxygen permeation and scratch resistance.
  • the coating of materials allows the tailoring of the surface properties thereof. For instance, a coating can change the colour of plastics, reduce the oxygen permeation through plastic films or enhance the abrasion resistance of leather.
  • Coatings can be applied by lacquering, CVD or PVD processes.
  • Lacquers for instance on the basis of hybrid polymers, can be applied by conventional lacquering techniques, such as spraying, rolling or application with a doctor knife.
  • the lacquer has been hardened (cured) in a second process step by heat treatment in a furnace or by irradiation with light.
  • barrier layers the typical thickness of such layers on the basis of hybrid polymers is about 8 ⁇ m.
  • Such a barrier layer improves the oxygen barrier properties usually by a factor of about 2.
  • conventional coating application methods the use of masks is necessary to apply the coating only at specific locations of the substrate.
  • conventional coatings based on hybrid polymers left much to be desired in connection with the surface properties of the coatings.
  • the barrier properties of the hybrid material coatings against oxygen proved insufficient for demanding applications.
  • EP 1 582 270 A1 aims at overcoming the drawbacks of conventional lacquering techniques, namely the insufficient utilization of the full potential of the hybrid materials.
  • the patent application relates to an atmospheric pressure plasma technology, in which a plasma is generated and maintained according to the Dielectric Barrier Discharge (DBD) technique.
  • the method comprises the steps of introducing the sample to be coated in the space between two electrodes, generating a plasma discharge between the electrodes and mixing aerosols containing hybrid inorganic-organic cross-linked pre-polymers into the plasma discharge.
  • the method of EP 1 582 270 A1 imposes severe restrictions on the size of the substrate to be coated. In the DBD techniques, the space, i.e. gap between the two electrodes is at most 5 mm, typically 2 to 3 mm.
  • the oxygen transmission rate (OTR) of a PET substrate of unspecified thickness could be reduced from 130 cm 3 /m 2 ⁇ d ⁇ bar to about 80 cm 3 /m 2 ⁇ d ⁇ bar by the coating. So, the OTR could be reduced by a factor of about 1.6 through the coating method of EP 1 582 270 A1 .
  • Plasma nozzles such as described in DE 195 32 412 A1 and DE 299 21 694 U1 are typically used to activate surfaces, e.g. to enhance the wettability of plastics.
  • WO 01/32949 plasma nozzles are exceptionally employed in the coating of surfaces.
  • a plasma jet is generated by passing a process gas through an excitation zone, and precursor material is fed into the plasma jet separately from the process gas.
  • the feeding of the precursor material can take place in the excitation zone of the plasma.
  • the precursor material is fed with a tube arranged downstream of the plasma nozzle exit. The precursor material is reacted with the aid of the plasma, and the reaction product is deposited on the surface.
  • the precursor materials used in WO 01/32949 are small molecules that are easy to volatilize. Hexamethyldisiloxane, tetraethoxysilane and propane are specifically mentioned in the reference.
  • DE 10 2006 038 780 A1 is concerned with an apparatus and method for preparing anti-corrosion coatings.
  • Precursor materials are injected into the relaxing plasma generated in a plasma nozzle. In the plasma, the precursor is partially fragmented and impinges on the surface of the substrate, where it polymerizes to result in an anti-corrosion coating.
  • silicon-containing low-molecular species such as hexamethyldisiloxane (HMDSO) and tetraethoxysilane (TEOS), are used as precursor materials.
  • low molecular mass gaseous precursors such as hexamethyldisilane (HMDS), tetramethylsilane (TMDS) and HMDSO are injected as precursor materials into a plasma jet.
  • HMDS hexamethyldisilane
  • TMDS tetramethylsilane
  • HMDSO tetramethylsilane
  • DE 198 07 086 A1 also describes a plasma coating apparatus.
  • WO 2005/053862 relates to a process for coating a substrate with at least two layers.
  • the process essentially comprises three steps, namely in step (a) the application of a first layer comprising a first inorganic component, in step (b) the treatment of the first layer with a plasma, and in step (c) the application of a second layer to the first layer, wherein the second layer comprises a second inorganic component.
  • the plasma employed in step (b) is an active plasma generated in a plasma reactor.
  • sol-gel coatings or a layer deposited by plasma chemistry can be used as the first layer comprising a first inorganic component.
  • the sol is not cured through the exposure to plasma but by thermal treatment or irradiation.
  • the plasma treatment of the first layer in step (b) is stated as serving to ensure sufficient adhesion of the second layer.
  • a thin film of silicon oil is applied to a surface, and the film is subsequently treated in a plasma.
  • the plasma treatment is effected by placing the silicon oil-coated substrates between the electrodes of a plasma reactor and exposing them to the active plasma generated between the electrodes.
  • WO 93/24243 is concerned with apparatuses and methods for depositing barrier coatings on polymeric substrates, such as PET films.
  • HMDSO precursors are used to form such barrier coatings.
  • the barrier coatings are stated as reducing the oxygen permeance of the polymeric substrates.
  • the present inventors have surprisingly found that the above object can be attained by the distinct coating methods as recited in the independent claims 1 and 5 involving the use of a liquid comprising specific hybrid inorganic-organic pre-polymers and an atmospheric pressure plasma jet.
  • the present invention provides two alternative methods for coating a substrate with an inorganic-organic hybrid polymer material.
  • the first method which is sometimes referred to in this description as the "one-step method of the invention"
  • the coating method of the present invention comprises a step (i) of applying liquid comprising hybrid inorganic-organic pre-polymers on a surface of the substrate, and a step (ii) of exposing said surface, i.e. the surface of the substrate with the liquid applied thereon, to an atmospheric pressure plasma jet to cure the hybrid inorganic-organic pre-polymers.
  • This method will sometimes be denoted the "two-step method of the invention", below.
  • the term “coating methods of the invention” as occasionally used herein is understood as a collective term encompassing both, the one-step and the two-step method of the invention.
  • the coating methods of the invention allow the preparation of substrates coated with inorganic-organic hybrid polymer material, which coated substrates have physical properties, in particular oxygen barrier properties that are substantially improved e.g. over the coated materials obtained in EP 1 582 270 A1 .
  • the OTR values could be reduced in the one-step method of the invention with respect to the starting substrate by a factor of at least 10 through the coating, whereas the corresponding reduction was only about 1.6 when using the technique of EP 1 582 270 A1 .
  • This is highly unexpected, for the following reasons.
  • the electron density (plasma intensity) is higher in DBD plasmas than in plasma jets obtained in a plasma nozzle. Higher electron density will result in higher degree of ionization and fragmentation of precursors.
  • coated articles obtainable with the coating method of the invention can have an OTR of less than 5 cm 3 /m 2 ⁇ d ⁇ bar for 23 ⁇ m thick PET films as substrates.
  • the water vapor transmission rate (WVTR) could be improved from 12 to 9 g/d ⁇ m 2 through the coating.
  • the difference in electron density to a DBD plasma is even more significant in the relaxing plasma, i.e. the plasma jet outside the plasma nozzle, in which the liquid comprising the hybrid inorganic-organic pre-polymers is injected in the one-step method of the invention.
  • the significantly improved oxygen barrier properties of the coated substrates or coated articles of the invention are even more unexpected.
  • the full potential of the inorganic-organic hybrid polymers is utilized by curing in a plasma jet.
  • the oxygen barrier properties could be enhanced significantly over corresponding coatings cured conventionally, e.g. by heat treatment in a furnace or by irradiation with light.
  • the enhanced oxygen barrier properties are due to a higher degree of crosslinking/curing of the inorganic-organic hybrid polymer material obtained in the two-step method of the present invention. This could be confirmed by NMR measurements.
  • coated substrates as meant herein refer to coated articles of arbitrary size and shape.
  • the coated substrates/articles obtained with the coating methods of the invention excel in their surface properties, in particular in their oxygen barrier properties.
  • a plasma coating apparatus comprising a plasma nozzle having a nozzle exit and a precursor feeding unit arranged downstream of the nozzle exit according to the preamble of Claim 7 is known from WO 01/32949 .
  • the plasma coating apparatus of the present invention is characterized by the feature of the precursor feeding unit being a liquid spray nozzle, the specific horizontal distance between the central axis of the plasma nozzle and the exit of the liquid spray nozzle, and the distinct opening diameter of the exit of the liquid spray nozzle.
  • the plasma coating apparatus according to the present invention is specifically adapted for use in the one-step coating method of the invention.
  • the atmospheric plasma pressure jet is generated by a plasma nozzle having a nozzle exit.
  • an atmospheric pressure plasma nozzle is used for generating the atmospheric pressure plasma jet.
  • the "atmospheric pressure plasma jet” is a plasma jet that is generated, maintained and operated at approximately atmospheric pressure.
  • the plasma nozzle for use in the present invention will be further illustrated by reference to Fig. 3 .
  • the plasma nozzle 4 is shown as a part of a plasma coating apparatus 10.
  • a plasma nozzle that can be used with benefit in the present invention has an electrically conductive housing 12, which is preferably elongated and is more preferably a tubular housing.
  • the housing 12 forms a nozzle channel 13 through which a working gas is flowing.
  • An electrode 14 is provided, preferably coaxially, in the nozzle channel 13.
  • a tube 16 of dielectric material, for instance a ceramic tube is inserted in the nozzle channel.
  • a voltage is applied between the electrode 14 and the housing 12. It proved to be advantageous to the formation of the plasma, when the voltage is pulsed.
  • the pulse frequency is not specifically limited and can be 5 to 100 kHz, with the range of 10 to 50 kHz being preferred.
  • a working gas 20 is fed to the nozzle channel 13 through a conduit 22, preferably such that the working gas shows a twisted flow through the channel. Such flow of the working gas can be achieved by way of a twisting device 17, which can be a plate having openings.
  • a twisting device 17 can be a plate having openings.
  • working gases 20 are useful in plasma nozzles. For instance, air, nitrogen, oxygen, ammonia (NH 3 ), hydrogen sulfide (H 2 S), noble gases, hydrogen and mixtures thereof can be used.
  • the preferred noble gas is argon.
  • the arc-like plasma discharge runs from the tip of the central electrode 14 essentially in axial direction of the nozzle channel 13 to the counter electrode 24, which is earthed like the housing. As a result, a plasma jet 2 is generated below the nozzle exit 5.
  • the operating mode of a plasma nozzle is known to the skilled person and is for instance further described in DE-A-195 32 412 and DE-U-299 21 694 .
  • the plasma nozzle for use in the method and plasma coating apparatus of the present invention is not particularly limited. According to a preferred embodiment, plasma nozzles, such as described in DE-A-195 32 412 or DE-U-299 21 694 , are used. More preferably, plasma nozzles are employed, which are within the scope of DE-A-195 32 412 , especially commercially available standard-single nozzles of the firm Plasmatreat (Germany).
  • the plasma jet is preferably a jet of a so-called “relaxing” plasma (occasionally also referred to as a “relaxed” plasma in the literature).
  • the "relaxing" plasma in the plasma jet is oftentimes also referred to as “after-glow” plasma.
  • the plasma is located outside the excitation zone which is confined by the electrodes, preferably the housing. This is different from so-called “active” plasma, which is generally understood to refer to a plasma which is located inside the space that is confined by the electrodes, wherein one electrode is usually the housing.
  • hybrid inorganic-organic pre-polymers comprised in a liquid are converted to inorganic-organic hybrid polymer material by the action of a plasma jet.
  • hybrid inorganic-organic pre-polymers for use in the present invention will be described in more detail.
  • the hybrid inorganic-organic pre-polymers will occasionally simply be referred to as "hybrid pre-polymers" or "pre-polymers” in the present application.
  • hybrid inorganic-organic pre-polymer refers to a pre-polymer comprising both, inorganic and organic regions that can also be referred to as inorganic and organic domains.
  • the inorganic regions comprise elements that are generally referred to as inorganic elements, namely Si, B, Al, P, Sn, Pb, the transition metals, lanthanides and actinides.
  • the inorganic region of the hybrid inorganic-organic pre-polymers for use in the coating methods of the present invention comprises, or is composed of, M-O-M-units, with M representing Si, B, Al, P, Sn, Pb, a transition metal, a lanthanide or an actinide, preferably Si, Ti, Zr or Al.
  • M representing Si, B, Al, P, Sn, Pb, a transition metal, a lanthanide or an actinide, preferably Si, Ti, Zr or Al.
  • the organic regions in the hybrid inorganic-organic pre-polymers for use in the present invention typically consist of C, H, O, N, S and halogens.
  • pre-polymer is intended to indicate that the molar mass of the hybrid inorganic-organic pre-polymers is increased in the coating methods of the invention, in which they are converted by curing reactions (to be further described below) to inorganic-organic hybrid polymer material in and/or through the action of, the plasma jet.
  • the pre-polymers for use in the present invention have a molar mass of at least 500 g/mol, preferably at least 1,000 g/mol.
  • the molar mass refers to the average molar mass, more specifically the weight average molar mass M W .
  • the upper limit of the molar mass of the pre-polymers there are no particular limitations as to the upper limit of the molar mass of the pre-polymers, as long as this can be increased by the action of the plasma jet in the coating methods of the invention to form inorganic-organic hybrid polymer material.
  • the upper limit of molar mass is preferably 12,000.
  • the range of molar mass of the hybrid inorganic-organic pre-polymers for use in the present invention is according to a more preferred embodiment in the range of 1000 to 10,000.
  • the hybrid inorganic-organic pre-polymers for use in the present invention are preferably crosslinked pre-polymers.
  • the hybrid inorganic-organic pre-polymers for use in the present invention are obtainable by hydrolytic condensation of one or more hydrolytically condensable compounds of silicon and optionally other elements from the group consisting of B, Al, P, Sn, Pb, the transition metals, the lanthanides, and the actinides (collectively referred to as "hydrolytically condensable compounds" herein), and/or precondensates derived from the above mentioned compounds wherein 10 to 100% by mol, preferably 20 to 100% by mol, more preferably 40 to 100% by mol, in terms of monomeric compounds, of the hydrolytically condensable compounds are silanes represented by the general formula (I), SiX a R 4-a (I) wherein the groups and indices are the same or different and have the following meanings: R represents optionally substituted alkyl, alkenyl, aryl, alkylaryl, or arylalkyl having 1 to 50 carbon atoms; X represents hydrogen, halogen, hydroxy,
  • hydrolytically condensable precursors is intended to encompass the above hydrolytically condensable compounds and/or precondensates thereof, and the silanes of formula (I).
  • the precondensates derived from the hydrolytically condensable compounds means molecules resulting from condensation of from 2 to 6, preferably 3 to 4 individual molecules of hydrolytically condensable compounds.
  • the group X in the silanes of formula (I) is hyrolyzable.
  • an organic network is formed in the pre-polymers, and through the groups X and, if applicable, the hydrolytically condensable compounds, an inorganic network having M-Q-M-units with M representing Si, B, Al, P, Sn, Pb, transition metal, lanthanide or actinide, preferably Si, Ti, Zr or Al is formed in the pre-polymers for use in the present invention.
  • the hydrolytically condensable compounds are represented by the following formula (II): M(OR 1 ) b (II) wherein M represents Si, Ti, Zr or Al, and b represents the valence of M, i.e. 4 in the case of Si, Ti and Zr, and 3 in the case of Al; and R 1 is substituted or unsubstituted alkyl, preferably C 1-6 alkyl, more preferably C 1-4 alkyl. Most preferably, R 1 is unsubstituted C 1-6 alkyl, especially unsubstituted C 1-4 alkyl, namely, methyl, ethyl, propyl or butyl.
  • Examples of the hydrolytically condensable compounds of formula (II) and precondensates derived therefrom are, without limitation, the following:
  • the hydrolytically condensable compounds for use in the present invention may bear an organic complex ligand.
  • hydrolytically condensable compounds examples include:
  • a preferred group within the silanes of formula (I) is represented by the following formula (III): Si(OR 2 ) c R 3 4-c (III)
  • R 2 represents alkyl, preferably C 1-6 alkyl, more preferably C 1-4 alkyl, namely, methyl, ethyl, propyl or butyl.
  • the index c represents 2 or 3.
  • the group(s) R 3 in formula (III) independently represent optionally substituted C 1-10 , preferably C 3-8 alkyl; optionally substituted C 2-10 , preferably C 2-6 alkenyl; or optionally substituted C 3-10 , preferably C 6-10 aryl.
  • the aryl group R 3 is especially phenyl.
  • the optional substitutents of the alkyl or aryl group R 3 are not specifically limited and can be selected from amino (including monoalkyl- and dialkylamino), mercapto, halo (in particular fluoro or chloro), ammonio (including mono-, di- and trialkylammonio), and anhydrido.
  • the counter ion of the ammonio group is not specifically limited in kind and can for instance be chloride or acetate.
  • Each of the above substituents can optionally be further substituted, preferably by the above substituents.
  • the substituents can comprise -O-, -C(O)-, -CO(O)-, -C(O)O- linkages.
  • the groups R 3 are nonreactive, in particular non-polymerizable groups, but which can impart certain chemical properties to the inorganic-organic hybrid polymer material coating, which will be formed from the hybrid inorganic-organic pre-polymers in the coating methods of the invention.
  • Me represents methyl
  • Et represents ethyl
  • Pr represents propyl
  • Bu represents butyl in the present specification.
  • the silanes of formula (I) or (III) it is preferable for the silanes of formula (I) or (III) to have at least one group R and R 3 , respectively, which has, as a substituent, a polymerizable functional group, i.e. a group which can undergo polymerization in the liquid comprising hybrid inorganic-organic pre-polymers and/or in the plasma jet during the coating methods of the invention.
  • the groups R or R 3 preferably comprise 1 to 3 of such functional groups, especially in terminal positions of the groups R/R 3 .
  • an additional organic polymer network can be formed in the hybrid inorganic-organic pre-polymers and eventually in the inorganic-organic hybrid polymer material.
  • the polymerizable functional groups can be selected from vinyl, glycidyl, acryl, methacryl and allyl. Examples of silanes of formula (I) or (III) having such terminal polymerizable groups are given without restriction to generality, below.
  • groups R and/or R 3 having at least one polymerizable functional group are those exemplified in EP 0 802 218 A2 , page 4, line 20 through page 11, line 34.
  • silanes of formula (I) having at least one group R comprising at least one polymerizable functional epoxy group are given at page 11, lines 35 to 49 of EP 0 802 218 A2 .
  • the hybrid inorganic-organic pre-polymers for use in the coating methods of the invention are obtainable from tetramethoxysilane, tetraethoxysilane, Dyansil 40®, zirconium-tetrapropoxide, aluminium-tributoxide, titaniumtetraethoxide, aluminium-dibutoxide ethylacetoacetate, zirkonium-tripropoxide methylacrylate, propyltrimethoxysilane, trifluoropropyl-triethoxysilane, octyltriethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane mercaptopropyltrimethoxy-silane, tridecafluorotriethoxysilane, aminopropyltriethoxy-silane, trimethylammonium-propyltrimethoxysilane, octadecyld
  • the hydrolytically condensable precursors will undergo hydrolysis and condensation, and possibly at least partial polymerization (in the case of groups R comprising polymerizable functional groups) so as to form hybrid inorganic-organic pre-polymers in the liquid.
  • the condensation reaction resulting in the pre-polymers is preferably carried out in accordance with the sol-gel process.
  • the hydrolysis and condensation to give hybrid inorganic-organic pre-polymers for use in the present invention is carried out by adding to the hydrolytically condensable precursors the necessary amount of water at room temperature or under cooling, and stirring the resultant mixture.
  • the hydrolytically condensable precursors can be present dissolved in a suitable solvent.
  • the solvent are, apart from aliphatic C 1-6 alcohols such as ethanol or i-propanol, ketones, preferably dialkyl ketones such as acetone or methylisobutyl ketone, ethers, preferably dialkyl ethers such as diethyl ether or dibutyl ether, THF, amides, esters, in particular ethyl acetate, dimethyl formamide, amines, in particular triethylamine, and suitable mixtures thereof.
  • the liquid comprising hybrid inorganic-organic pre-polymers is an aliphatic C 1-6 alcohol.
  • suitable catalysts may be added to the liquid.
  • further compounds may be added to the liquid comprising inorganic-organic hybrid pre-polymers, before this is exposed to the plasma jet.
  • examples of such compounds may be organic coating forming materials such as carboxylates, methacrylates, acrylates, styrenes, methacrylonitriles, alkenes and dienes, e.g.
  • (meth)acrylate(s) is a collective term for acrylate(s) and methacrylate(s).
  • the liquid comprising hybrid inorganic-organic pre-polymers used in the coating methods of the invention is one that is sold under the trademark ORMOCER ® .
  • the material of the substrate is not specifically limited in kind, as long as it does not disintegrate or decompose in the plasma jet.
  • the substrate may comprise, or consist of, metal, plastics (such as PET, i.e. polyethylene terephthalate, or polycarbonate), cellulosic material, leather, or ceramics.
  • the form and shape of the substrates to be coated in the coating methods of the invention is also not specifically limited. Examples of the substrates are films, fibres, powders or moulded articles. Further examples of useful substrates are materials already having at least one barrier layer. In this case, the provision of an additional coating layer by means of the coating methods of the invention results in a multilayer structure.
  • the coating methods of the invention can be used in the field of packaging and technical applications, e.g. for providing barrier films for flexible displays or photovoltaic panels, or abrasion resistant coatings for transparent polymers, e.g. displays for mobile phones, or leather, as well as functional coatings for paper and textile finishing.
  • the present invention is also directed to the coated substrates as such that are obtainable by the coating methods of the invention, i.e. the one-step method or the two-step method.
  • the coated substrates can have an Oxygen Transmission Rate (OTR) as low as ⁇ 5 cm 3 /m 2 ⁇ d ⁇ bar for 23 ⁇ m thick PET substrates. Therefore, the coating methods of the invention are excellently suited for providing oxygen barrier layers, e.g. in the field of food or beverage packaging.
  • a typical coated substrate in accordance with the present invention would be a packaging film, or an encapsulation film for solar panels or OLEDs, which film has been subjected to the coating methods of the invention.
  • the plasma coating apparatus comprising the plasma nozzle 4 and the liquid spray nozzle 6 is moved relative to the substrate 1 to be coated.
  • the relative movement of the plasma nozzle 4 and the liquid spray nozzle 6 (jointly forming the plasma coating apparatus 10) with respect to the substrate 1 is shown in Fig. 1 by the horizontal arrow 30.
  • the hybrid inorganic-organic pre-polymers included in the liquid 3 that is injected in the plasma jet 2 will deposit as an inorganic-organic hybrid polymer material 9 on the substrate 1 thus forming a coated substrate 7.
  • the inorganic-organic hybrid polymer material will sometimes be denoted as "hybrid polymer material”.
  • the relative velocity of the plasma coating apparatus 10 (comprising the plasma nozzle 4 and the liquid spray nozzle 6) and the substrate 1 is not specifically limited and can for instance be 0.1 to 300 m/min.
  • the relative velocity is 1 to 30, more preferably 2 to 20 m/min.
  • the hybrid inorganic-organic pre-polymers comprised in the liquid injected in the plasma jet will undergo curing to give inorganic-organic polymer material.
  • This requires the evaporation of the liquid, e.g. the solvent surrounding the hybrid inorganic-organic pre-polymers.
  • the evaporation heat consumed thereby will reduce the local energy within the plasma jet. This is different from the methods described in the prior art, such as WO 01/32949 , wherein precursor gases rather than liquids are fed to a plasma zone.
  • the curing reactions occurring in the coating methods of the invention within the plasma jet are different from those of the prior art.
  • the influence of the plasma will lead, e.g. through bond cleavage, ring opening reactions and polymerisation (for instance of polymerizable functional groups) to an increase of the molar mass of the hybrid inorganic-organic pre-polymers to give hybrid polymer material.
  • curing reactions may occur on the surface of the substrate even after the plasma jet has been moved further along the surface of the substrate.
  • the curing of the hybrid inorganic-organic pre-polymers in the plasma jet to give inorganic-organic hybrid polymer material can be controlled, and the physical properties, such as the barrier properties, in particular oxygen barrier properties, of the inorganic-organic hybrid polymer material can be fine-tuned with ease in the coating methods of the invention.
  • Such parameters are the selection of the particular hybrid inorganic-organic pre-polymer, and the concentration of the pre-polymers in the liquid to be injected in the plasma jet (in the one-step method) or to be applied on a surface of the substrate (in the two-step method).
  • the form in which the liquid comprising hybrid inorganic-organic pre-polymers is injected in the plasma jet was found to influence the characteristics of the resultant inorganic-organic hybrid polymer material.
  • the liquid is injected in the form of an aerosol that is sprayed in the plasma jet in the one-step method of the invention.
  • a droplet size of the liquid in the range of 0.5 to 100 ⁇ m proved to be particularly beneficial to the properties of the resultant inorganic-organic hybrid polymer material.
  • Aerosols of liquid having a droplet size within that range can be generated with a liquid spray nozzle, which will be further illustrated below, using a suitable carrier gas, such as air or nitrogen.
  • a suitable carrier gas such as air or nitrogen.
  • the distance g along a parallel to the central axis 11 of the plasma nozzle, between the exit of the liquid spray nozzle 5 and the surface of the substrate 1 is preferably in the range of 4 to 50 mm, more preferably 10 to 30 mm. Most preferably, the distance g is about 20 mm.
  • the distance d between the nozzle exit 5 of the plasma nozzle 4, and the exit of the liquid spray nozzle 6, along a parallel to the central axis 11 of the plasma nozzle is 2 to 30 mm, more preferably 5 to 15 mm, most preferably to about 10 mm.
  • the horizontal distance f between the central axis 11 of the plasma nozzle 4 and the exit of the liquid spray nozzle 6 is preferably 2 to 50 mm, more preferably 10 to 30 mm, and most preferably it is about 20 mm.
  • the angle between the central axis 11 of the plasma nozzle 4 and the central axis of the liquid spray nozzle is preferably 80 to 100°, more preferably 85 to 95°, and most preferably it is approximately 90° as is shown in Figs. 1 and 3 .
  • the parameters d and f in particular will have some influence on the properties of the hybrid polymer material obtained in the one-step method.
  • the activity of the plasma in the plasma jet will decrease with increasing d resulting in less fragmentation of the pre-polymers injected in the plasma jet.
  • the distance f this will influence the homogeneity of the injection of the liquid comprising the pre-polymers. The larger the distance f, the more inhomogeneous will be the feeding in the plasma jet due to an increasing divergence angle.
  • an inorganic-organic hybrid polymer material having outstanding oxygen barrier properties can be obtained when f is between 10 and 30 mm, d is between 5 and 15 mm, the angle between the central axis 11 of the plasma nozzle 4 and the central axis of the liquid spray nozzle 6 is approximately 90°, and the liquid comprising hybrid inorganic-organic pre-polymers is injected in the plasma jet in the form of an aerosol, such as having a droplet size of 0.5 to 100 ⁇ m.
  • the distance g may be 4 to 50 mm, and preferably it is 10 to 30 mm.
  • the plasma-coating apparatus is suitable to, and specifically adapted to, carrying out the one-step coating method of the invention.
  • it is equipped with a liquid spray nozzle for feeding the precursors, in particular the liquid comprising hybrid inorganic-organic pre-polymers.
  • the liquid spray nozzle of the plasma coating apparatus is preferably designed such that liquid, such as liquid comprising pre-polymers can be injected into a plasma jet exiting the plasma nozzle through the nozzle exit. This is illustrated in Fig. 3 .
  • the liquid spray nozzle 6 is different from the tube shown e.g. in Fig. 1 of WO 01/32949 , which serves to feed gases.
  • the liquid spray nozzle is, as suggested by the name, a nozzle for spraying liquids.
  • the opening diameter of the exit of said nozzle is less than 1 mm.
  • Specific examples of the liquid spray nozzles for use in the plasma coating apparatus according to the present invention are "Meinhard Zerstauber TR-30-A1 (A3)", available from Spectec GmbH (Erding, Germany) and “Burgener Zerstauber PMM-4000", obtainable from Maassen GmbH (Reutlingen, Germany). These liquid spray nozzles, which are commercially available, can be used with particular benefit in the plasma coating apparatus and the one-step coating method according to the present invention.
  • the liquid spray nozzle 6 is preferably arranged in the plasma coating apparatus of the invention such that the distances d, and the angle between the central axis 11 of the plasma nozzle and the central axis of the liquid spray nozzle 6 are in the ranges that have been defined for the one-step method of the invention, above.
  • the distance f is preferably about 20 mm.
  • step (i) liquid comprising hybrid inorganic-organic pre-polymers 3 is applied on a surface of the substrate 1.
  • Fig. 2b wherein the application of the liquid 3 is symbolized by pouring the liquid contained in a vessel onto the substrate resulting in a liquid 8 applied on the substrate.
  • the method of applying the liquid 3 can be conventional methods of applying lacquer, for instance spraying, rolling, or applying by using e.g. a plate, knife or doctor knife.
  • the vessel containing liquid 3 for pouring the liquid on the substrate 1 is moved relative to the substrate 1.
  • the liquid 8 applied on the substrate is subsequently exposed in step (ii) to a plasma jet 2, which is generated in Fig. 2c by a plasma nozzle 4.
  • the hybrid inorganic-organic pre-polymers in the applied liquid 8 are cured to give (cured) inorganic-organic hybrid polymer material 9.
  • the plasma nozzle 4 and the substrate 1 are moved relative to each other at a speed that is not particularly limited but is preferably 0.5 to 200 m/min, more preferably 5 to 100 m/min and especially 10 to 20 m/min.
  • Said relative velocity of the substrate 1 and the plasma nozzle 4 in the two-step coating method of the invention can also be referred to as a scanning speed.
  • the distance g as illustrated in Fig. 3 i.e. the distance between the nozzle exit 5 of the plasma nozzle 4 along a parallel line to the central axis 11 thereof and the substrate 1 is preferably in the range of 3 to 50 mm in the two-step method. More preferably, the distance g is 4 to 20 mm and especially 5 to 10 mm.
  • the time between application step (i) and exposure step (ii) may be in the range of seconds but can also be in the range of days.
  • radicals, ions, electrons, species in excited states and photones act collectively.
  • the combined effect of these species will lead to a high degree of crosslinking within the inorganic-organic hybrid polymer material upon curing.
  • the high degree of crosslinking is reflected in the good barrier values of the hybrid polymer material coating.
  • the above combined effect of different species does not take place in the conventional curing treatments such as e.g. by thermal oven treatment.
  • the plasma generated by the plasma jet used in the two-step coating method of the invention is a relaxing plasma
  • the distribution of plasma species therein is rich on radicals and species in excited states, while it has a comparably low content of ions and electrons. Radicals are expected to be particularly efficient in crosslinking upon curing to give the inorganic-organic hybrid polymer material. Consequently, the two-step coating method of the invention wherein the substrate having liquid 8 applied thereon is exposed to a relaxing plasma of a plasma jet will yield hybrid polymer materials having particularly outstanding barrier properties.
  • a plasma coating apparatus was used, in which the liquid spray nozzle was arranged in a horizontal distance f of 20 mm with respect to the central axis of the plasma nozzle, and at a distance d to the nozzle exit of the plasma nozzle along a parallel to the central axis of the plasma nozzle of 10 mm.
  • the liquid spray nozzle was made of glass, and the exit of the liquid spray nozzle had an opening diameter of 400 ⁇ m.
  • An aerosol of an ORMOCER ® liquid was generated by mixing the liquid with nitrogen as a carrier gas. The thus-created aerosol was sprayed in the plasma jet through the liquid spray nozzle.
  • a polycarbonate plate was used as a substrate. The substrate was moved at a velocity of 10 m/min through the plasma jet. The distance g between the substrate surface and the nozzle exit was 20 mm.
  • the ORMOCER ® liquid is applied with a doctor knife on a PET film having a thickness of 23 ⁇ m until a coating thickness of 10 ⁇ m was obtained. Then, the substrate with the liquid applied thereon was scanned with a plasma nozzle with the distance between the nozzle exit and the film g being 5 mm at a velocity of 20 m/min, to cure the ORMOCER ® and obtaining an inorganic-organic hybrid polymer material coating.
  • the measurement of the Oxygen Transmission Rate (OTR) (in accordance with DIN 53380) was reduced 10-fold in comparison to a corresponding coating, which was cured in a furnace at 120 °C for 2 hours.

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Claims (9)

  1. Procédé de revêtement d'un substrat (1) avec un matériau polymère hybride inorganique-organique (9), le procédé comprenant l'injection d'un liquide comprenant des prépolymères inorganiques-organiques hybrides (3) dans un jet de plasma à pression atmosphérique (2), et l'exposition d'une surface du substrat (1) audit jet de plasma (2),
    dans lequel le jet de plasma (2) est généré par une buse de plasma (4) ayant une sortie de buse (5), et le liquide comprenant les prépolymères inorganiques-organiques hybrides (3) est injecté dans le jet de plasma (2) après avoir quitté la sortie de buse (5) et avant de heurter la surface du substrat (1), et
    dans lequel les prépolymères inorganiques-organiques hybrides peuvent être obtenus par condensation hydrolytique d'un ou plusieurs composés de silicium condensables hydrolytiquement et facultativement d'autres éléments dans le groupe consistant en B, Al, P, Sn, Pb, les métaux de transition, les lanthanides, et les actinides, et/ou des précondensats dérivés des composés susmentionnés, dans lequel 10 à 100 % en mole, en termes de composés monomériques, des composés condensables hydrolytiquement sont des silanes représentés par la formule générale (I),

            SiXaR4-a     (I)

    où les groupes et indices sont identiques ou différents et ont les significations suivantes :
    R = alkyle, alcényle, aryle, alkylaryle ou arylalkyle facultativement substitué ayant 1 à 50 atomes de carbone, X = hydrogène, halogène, hydroxy, alcoxy, acyloxy, alkylcarbonyle, alcoxycarbonyle, ou NR'2 avec R' = hydrogène, alkyle ou aryle ; a = 1, 2 ou 3,
    caractérisé en ce que les prépolymères inorganiques-organiques hybrides ont une masse moléculaire moyenne en poids d'au moins 500 g/mole.
  2. Procédé selon la revendication 1, dans lequel le liquide comprenant les prépolymères inorganiques-organiques hybrides (3) est injecté dans le jet de plasma (2) par l'intermédiaire d'une buse de pulvérisation de liquide (6).
  3. Procédé selon la revendication 1 ou 2, dans lequel la distance (d) le long d'une parallèle à l'axe central (11) de la buse de plasma (4), entre la sortie de la buse de pulvérisation de liquide (6) et la sortie de buse (5) de la buse de plasma (4) est dans la plage de 2 à 30 mm, de préférence 5 à 15 mm.
  4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel le liquide comprenant les prépolymères inorganiques-organiques hybrides (3) est injecté dans le jet de plasma (2) sous la forme d'un aérosol.
  5. Procédé de revêtement d'un substrat (1) avec un matériau polymère hybride inorganique-organique (9), le procédé comprenant les étapes suivantes :
    (i) l'application d'un liquide comprenant des prépolymères inorganiques-organiques hybrides (3) sur une surface du substrat (1), et
    (ii) l'exposition dudit substrat à un jet de plasma à pression atmosphérique (2), pour durcir lesdits prépolymères inorganiques-organiques hybrides pour donner un matériau polymère hybride inorganique-organique (9),
    dans lequel les prépolymères inorganiques-organiques hybrides peuvent être obtenus par condensation hydrolytique d'un ou plusieurs composés de silicium condensables hydrolytiquement et facultativement d'autres éléments dans le groupe consistant en B, Al, P, Sn, Pb, les métaux de transition, les lanthanides, et les actinides, et/ou des précondensats dérivés des composés susmentionnés, dans lequel 10 à 100 % en mole, en termes de composés monomériques, des composés condensables hydrolytiquement sont des silanes représentés par la formule générale (I),

            SiXaR4-a     (I)

    où les groupes et indices sont identiques ou différents et ont les significations suivantes :
    R = alkyle, alcényle, aryle, alkylaryle ou arylalkyle facultativement substitué ayant 1 à 50 atomes de carbone, X = hydrogène, halogène, hydroxy, alcoxy, acyloxy, alkylcarbonyle, alcoxycarbonyle, ou NR'2 avec R' = hydrogène, alkyle ou aryle ; a = 1, 2 on 3,
    dans lequel les prépolymères inorganiques-organiques hybrides ont une masse moléculaire moyenne en poids d'au moins 500 g/mole, et
    dans lequel le jet de plasma (2) est généré par une buse de plasma (4) et le substrat (1) avec le liquide appliqué est balayé avec ladite buse de plasma.
  6. Procédé selon la revendication 5, dans lequel la distance (g) le long d'une parallèle à l'axe central (11) de la buse de plasma (4) entre la sortie de buse (5) de la buse de plasma (4) et le substrat (1) est dans la plage de 3 à 40 nm, de préférence 3 à 20 mm.
  7. Appareil de revêtement au plasma (10) comprenant une buse de plasma (4) ayant un axe central (11) et une sortie de buse (5), et une unité d'alimentation en précurseur agencée en aval de la sortie de buse (5),
    caractérisé en ce que l'unité d'alimentation en précurseur est une buse de pulvérisation de liquide (6), en ce que la distance horizontale (f) entre l'axe central (11) et la sortie de la buse de pulvérisation de liquide (6) est entre 10 et 30 mm, et en ce que le diamètre d'ouverture de la sortie de la buse de pulvérisation de liquide (6) est inférieur à 1 mm.
  8. Appareil de revêtement au plasma (10) selon la revendication 7, dans lequel la buse de pulvérisation de liquide (6) est conçue de façon à être capable de générer un aérosol ayant une taille moyenne de gouttelettes dans la plage de 0,5 à 100 µm.
  9. Utilisation de l'appareil de revêtement au plasma (10) selon la revendication 7 ou 8 dans un procédé de revêtement tel que défini dans l'une quelconque des revendications 1 à 4.
EP09166450.8A 2009-07-27 2009-07-27 Procédés de revêtement utilisant un jet de plasma et appareil de revêtement au plasma Not-in-force EP2279801B1 (fr)

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EP09166450.8A EP2279801B1 (fr) 2009-07-27 2009-07-27 Procédés de revêtement utilisant un jet de plasma et appareil de revêtement au plasma

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WO2012007388A1 (fr) * 2010-07-12 2012-01-19 Solvay Sa Procédé de dépôt plasma de polymère
WO2015005885A1 (fr) * 2013-07-08 2015-01-15 Deltamed Yasam Bi̇li̇mleri̇ Ve Plazma Teknoloji̇leri̇ Ar-Ge Sanayi̇ Ve Ti̇caret Anoni̇m Si̇rketi̇ Procédé de préparation de surface par un système de plasma à pression atmosphérique pour l'immobilisation de biomolécules et surface obtenue par ce procédé
US20150349307A1 (en) * 2014-05-27 2015-12-03 GM Global Technology Operations LLC Method for preparing a coated lithium battery component
WO2018017058A1 (fr) 2016-07-19 2018-01-25 Hewlett-Packard Development Company, L.P. Systèmes d'impression
WO2018017063A1 (fr) 2016-07-19 2018-01-25 Hewlett-Packard Development Company, L.P. Têtes de traitement au plasma
US10532582B2 (en) 2016-07-19 2020-01-14 Hewlett-Packard Development Company, L.P. Printing systems
DE102017216139B3 (de) * 2017-09-13 2019-02-28 Innovent E.V. Verfahren zur Herstellung einer Schicht

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