EP1230042B1 - Couche a fonctionnalisation selective de la surface - Google Patents

Couche a fonctionnalisation selective de la surface Download PDF

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Publication number
EP1230042B1
EP1230042B1 EP00984979A EP00984979A EP1230042B1 EP 1230042 B1 EP1230042 B1 EP 1230042B1 EP 00984979 A EP00984979 A EP 00984979A EP 00984979 A EP00984979 A EP 00984979A EP 1230042 B1 EP1230042 B1 EP 1230042B1
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EP
European Patent Office
Prior art keywords
layer
plasma
substrate
grafting
monomers
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP00984979A
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German (de)
English (en)
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EP1230042A2 (fr
Inventor
Claus-Peter Klages
Rudolf Thyen
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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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    • 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
    • B05D1/60—Deposition of organic layers from vapour phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • 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
    • B05D7/52—Two layers

Definitions

  • the present invention relates to a layer which by means of a plasma-assisted Method has been obtained, the surface of this Layer has been selectively functionalized, a method of preparation such a layer and its use.
  • the coating of substrates by means of plasma-assisted processes is on known.
  • precursor the coating precursor materials
  • the individual procedures differ here in the type of plasma generation and in the choice of process conditions, especially the pressure.
  • a thin plasma polymer layer deposited on a pretreated substrate wherein as precursor for the polymer layer an organic Compound such as methylsilane, trimethylsilane, etc. is used.
  • a coating layer of an epoxyamine or epoxy-polyester melamine is used as a corrosion resistant protective layer for ungalvanized Metal surfaces used.
  • Prec RSOR u can in this case for example, hydrocarbons, silicon-containing compounds, boron or phosphorus-containing compounds or metal compounds in question. It is advantageous that in these processes, the layer deposition can be carried out at high pressures, for example at atmospheric pressure, and can be dispensed with a complex vacuum apparatus, as they are essential in low-pressure process.
  • WO 97/22631 relates to a multi-layer system, wherein the individual Layers are deposited by plasma discharge. This is a three-dimensional network formed with a high number of functional groups.
  • Plasma deposited layers can fulfill a variety of tasks. she can as corrosion protection layers the passage of corrosive media, especially oxygen and water, prevent and / or as electrical Isolation layers act. In addition, they can find bonding agents between the Substrate and further applied to the plasma deposited layer Layers such as lacquer layers, adhesive layers, primer layers or for imprints. Frequently, if a combination of different Properties is desired, not a single layer but a layer system proposed as a gradient or multilayer system can be trained.
  • a layer surface thus obtained contains a mixture many functional groups, as by reaction during the plasma discharge be formed. It has been shown that in the case of hydroxyl-containing Precursom the surface oxygen not only in the oxidation state having the hydroxyl group, but also in other oxidation states. Also, it is not possible by means of plasma deposition to apply sensitive groups such as epoxy groups on the surface, as these groups usually under the conditions of the procedure be destroyed. In addition, it has been shown that the occupancy of Surface with functional groups is low. That is, it is with the conventional plasma method not possible, controlled a Surface modification with functional groups on the layer, wherein the type of functional groups are selectively selected can and additionally achieves a sufficiently dense surface coverage can be.
  • these layers should be functionalized such that they due to a suitable selection of functional groups on the Surface are applied, an optimal binding / adhesion of additional layers to be applied thereto, in particular organic Layers, ensure.
  • This object is achieved by a layer that is supported by a plasma Method has been deposited on a substrate, wherein the surface of the layer is selectively functionalized by grafting monomers has been.
  • the present invention relates to a method for producing a Layer with selectively functionalized surface on a substrate, thereby characterized in that the layer on the substrate by means of a plasma-assisted Deposition process generated and the surface of the layer is selectively functionalized by grafting monomers.
  • the term "selectively functionalized” means that by suitable choice of the monomers on the surface of a plasma-deposited Layer according to desire and purpose functional Groups can be applied.
  • the nature of the monomers is subject in this case no restriction so that in particular functional Groups involved in the conditions of deposition of the layer in the plasma would be destroyed or otherwise react to the surface the deposited layer can be applied.
  • the end group E can be any component that leads to a chain termination reaction.
  • E can be hydrogen.
  • the chain length or monomer number n of the grafted-on monomer chain can be influenced by suitable selection of the process parameters such as temperature, process duration, irradiation intensity, partial pressure of the monomer in gas phase polymerization or volume fraction and presence of inhibitors in liquid phase polymerization. In this way, by choosing a monomer M with suitable functional groups, it is possible to cause a plurality of these functional groups to be covalently coupled to the polymer surface, thus varying the properties of the polymer surface as required.
  • the surface can be optimal for the adhesion of another Layer, a paint, a primer, adhesive or other preferably be adapted to organic material. That is especially the case Case, when a functional group F of the monomers in turn with corresponding functional groups F 'of the subsequently applied layer can react.
  • It may be any layer as obtainable by conventional plasma enhanced techniques. It may be a few atomic layers of a hydrocarbon layer to a layer consisting of silicon, carbon and hydrogen, the layers may contain oxygen, nitrogen, sulfur, boron, phosphorus, halogens, for example, it may be a silicon oxide layer.
  • the layer it is possible to use all known compounds from the field of chemical vapor deposition, for example hydrocarbons, optionally with functional groups, silicon-containing compounds, compounds containing oxygen, nitrogen, boron, sulfur, halogen and / or phosphorus or metal compounds.
  • Preferred precursors are organic compounds.
  • Suitable examples are propargyl alcohol, tetramethylsilane, hexamethyldisiloxane, vinyltrimethoxysilane, phenyltrimethoxysilane, aminopropyltrimethoxysilane, mercaptopropyltrimethoxysilane, dimethyldichlorosilane, trimethylphosphite, trimethylborate, and especially methane, ethene and ethyne.
  • the layer thickness is typically in a range of 1 nm to 1 ⁇ m, preferably 5 nm to 100 nm.
  • the substrate material can in principle be chosen arbitrarily.
  • the inventive method is particularly suitable for applying a selectively functionalized surface layer on a metallic substrate.
  • the substrate to be coated may be, for example, aluminum, steel or a be galvanized steel sheet.
  • the substrate may have any shape. It can be a profile, profile tube, wire or plate or component an electronic component.
  • the surface can be conditioned specifically for the attachment / adhesion of another coating layer, wherein the functional groups or the monomer is selected depending on the layer material of the still applied coating layer, so that a firm connection between ground and coating is guaranteed.
  • Such further layers may be coatings, for example conformal coatings, lacquers with decoration function, paints, printing inks, adhesives, primers, etc.
  • these further layers consist of an organic material.
  • the type of monomers depends on the desired functionalization.
  • the inventive method is particularly suitable to do so, functional groups that are destroyed or remodeled in a plasma process would be to the surface of a plasma-deposited To bind layer.
  • suitable monomer compounds are Vinyl compounds, in particular acrylic acid, methacrylic acid and their Derivatives such as esters such as glycidyl methacrylate.
  • the monomer compounds may be used singly or in combination become.
  • the plasma deposited layer may be formed by any known plasma assisted process for layer deposition. It can be a low pressure or high pressure process. It can be a so-called cold plasma process.
  • Low pressure processes typically operate at pressures in the range of 0.01 Pa to 10 kPa. Glow discharges are particularly suitable for this, by DC voltages, AC voltages or microwaves can be maintained.
  • Suitable pressure ranges for the high pressure process are in the order of 10 4 Pa to 1.5 x 10 5 Pa.
  • High-pressure processes are, for example, barrier discharge or plasma generation by pulsed high-voltage arc discharge.
  • the layer deposition from a barrier discharge is known per se and for example in detail in DE 195 05 449 C2 or R. Thyen, A. Weber, C.-P. Klages, Surf. Coat. Technol. 97 (1997) 426-434 in detail as described herein for the purposes of the present invention express reference is made.
  • the monomers react with the reactive centers that are on the surface of the freshly formed layers.
  • the chain length that is, the number of monomers n grafted to a single reactive center of the surface can be controlled by the reaction conditions such as the number of end groups.
  • the invention thus also includes functionalized surfaces with graft molecule chains n> 1.
  • the monomers may be liquid, gaseous, aerosolized, with or without inhibitors and / or diluted with inert gas such as argon, nitrogen.
  • concentration can be determined by the vapor pressure. If necessary, it can be diluted with water.
  • the functionalization takes place without intermediate exposure the plasma deposited layer to the ambient atmosphere, to prevent premature reaction of the reactive centers.
  • the layer deposition (also called plasma deposition) and the grafting can take place spatially or temporally separated from one another. That is, the grafting may be done in the same device as the plasma deposition, or the plasma deposited layer substrate may be placed in a separate device or chamber set up for grafting. The grafting can take place after the plasma deposition.
  • a high coverage of the surface of the plasma-deposited layer with functional groups can be achieved (number of functional groups per surface unit).
  • occupancy densities in the range of 10 15 - 10 17 per cm 2 can be achieved with the present invention.
  • only coating densities of ⁇ 10 15 / cm 2 can generally be achieved for the abovementioned plasma polymer.
  • the functional groups or the graft molecules on the surface of the plasma deposited Layer a thin film similar to the Langmuir-Blodgett films.
  • the plasma deposited layer may be a single layer of homogeneous component composition or of a graded component composition, wherein the content and / or type of components may vary over the layer thickness. It may be a layer system that consists of several individual layers, which may also be provided here, if necessary, a graduation.
  • the figure shows schematically a device for layer deposition by means Barrier discharge.
  • the exemplary apparatus for performing the Schichtdeposition means Barrier discharge consists in principle of an electrode or electrode assembly 2 and a counter electrode 6 on which the substrate 5 is stored.
  • the electrode 2 can consist of an electrode arrangement with a plurality of individual electrodes, wherein an electrode arrangement with two individual electrodes 2 is shown in the figure.
  • the electrode 2 or the individual electrodes 2 are each surrounded by a dielectric barrier layer 3.
  • the dielectric barrier layer 3 may be made of alumina ceramic, for example consist.
  • the barrier discharge burns in the discharge space between the rod-shaped electrodes 2 on the one and the counter electrode 6 on the other side, the precursors for layer formation be introduced through the gas inlet 1.
  • filaments 4 arise interact with the substrate surface and in general have a diameter of 0.1 mm. Activation and deposition of the Precursors take place predominantly in the bases of the filaments 4.
  • the gap between electrodes 2 and counter electrode 6 is usually between 1 and 5 mm and corresponds to the length of the filaments.
  • the substrate is preferably moved back and forth, indicated in the figure by the arrows 7.
  • the layer deposition by a suitable pulsation the supply voltage for the discharge to be controlled, the individual pulses are made at intervals that are sufficient that the formed Charge carriers are neutralized in the gas space, thereby preventing will be that the following micro discharge in the same place as the previous training.
  • the layer deposition by means of barrier discharge usually in a pressure range of 0.1 to 1.5 bar and a voltage range of preferably at least 3 kV performed.
  • the amount of tension depends on the type and size of the used plant and after the process gas composition.
  • the Frequency of the alternating field can be in the range of 0.05 to 100 kHz.
  • the monomers M become instantaneous after the layer deposition in the barrier discharge outside of the Area of the barrier discharge to the substrate gaseous, liquid or as Aerosol allowed to act.
  • the monomers for both Formation of the thin layer and thus as precursors and at the same time as Monomer can be used for the grafting reaction.
  • Store here the monomers to the formed during the barrier discharge suitable reactive centers.
  • the grafting reaction takes place here in the Areas of the substrate between each filament or discharge channels lie. In the discharge channels there is a strong decomposition the monomers and in this way activation of the monomers to Film deposition. However, enough remains outside the filaments Monomer unaffected by the barrier discharge and stands for the grafting to disposal.
  • Both the uniformity and the efficiency of the grafting can be controlled by suitable pulsing of the supply voltage for the discharge.
  • the pulsation should be oriented in such a way that the grafted-on functional groups (monomers) are retained on the surface and are not destroyed in the course of further barrier discharges at this point.
  • the counter electrode becomes Oscillatory at a rate of 0.5 cm / s by the discharge emotional.
  • a plasma graft polymer has by codeposition deposited as a thin layer on the aluminum surface.
  • the coated surface is very hydrophilic, the surface tension is > 66 mN / m. She is after a 10-minute exposure of the coated Surface unchanged in concentrated potassium hydroxide solution.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Claims (21)

  1. Procédé de fabrication d'une couche à surface sélectivement fonctionnalisée,
    caractérisé en ce que,
    une couche est produite sur un substrat par dépôt en plasma et la surface de la couche est chimiquement sélectivement fonctionnalisée par greffage de monomères sur des centres réactifs à la surface de la couche.
  2. Procédé selon la revendication 1,
    caractérisé en ce que,
    le nombre n des monomères M, qui sont greffés sur un centre réactif, est supérieur à 1.
  3. Procédé selon l'une ou l'autre des revendications 1 ou 2,
    caractérisé en ce que,
    le matériau précurseur de revêtement pour le dépôt en plasma est au moins un composé qui est choisi parmi des composés qui contiennent, en plus du carbone et/ou du silicium, le cas échéant au moins un autre élément parmi l'oxygène, l'azote, le soufre, le bore, le phosphore, un halogène et l'hydrogène.
  4. Procédé selon la revendication 3,
    caractérisé en ce que,
    on utilise, pour le dépôt en plasma au moins un composé hydrocarboné et/ou un composé hydrocarboné comportant un groupe fonctionnel.
  5. Procédé selon la revendication 4,
    caractérisé en ce que,
       au moins un composé hydrocarboné est choisi parmi l'alcool propargylique, le tétraméthylsilane, l'hexaméthyldisiloxane, le vinyltriméthoxysilane, le phényltriméthoxysilane, l'aminopropyltriméthoxysilane, le mercaptopropyltriméthoxysilane le diméthyldichlorosilane, le phosphite de triméthyle, le borate de triméthyle, le méthane. l'éthène et l'éthyne.
  6. Procédé selon l'une quelconque des revendications précédentes,
    caractérisé en ce que,
       au moins un monomère pour la réaction de greffage est choisi parmi l'acide acrylique, l'acide méthacrylique, un dérivé de ces derniers ou un composé vinylique.
  7. Procédé selon la revendication 6,
    caractérisé en ce que,
    le dérivé est un ester, de préférence le méthacrylate de glycidyle.
  8. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que,
    le dépôt en plasma et le greffage sont effectués séparément l'un de l'autre dans l'espace et/ou dans le temps.
  9. Procédé selon l'une quelconque des revendications précédentes,
    caractérisé en ce que,
    le dépôt en plasma, et le cas échéant le greffage, sont effectués à des pressions se situant entre 0,01 Pa et 10 kPa.
  10. Procédé selon la revendication 9,
    caractérisé en ce que,
    on utilise, pour le dépôt en plasma, le plasma d'une décharge dans un gaz entretenue par une tension continue, une tension alternative ou des micro-ondes.
  11. Procédé selon l'une quelconque des revendications 1 à 8,
    caractérisé en ce que,
    le dépôt en plasma, et le cas échéant le greffage, sont effectués à des pressions se situant entre 10 kPa et 150kPa.
  12. Procédé selon la revendication 11
    caractérisé en ce que,
    le plasma est produit dans une décharge barrière diélectrique ou une décharge d'arc pulsé.
  13. Couche à surface sélectivement fonctionnalisée,
    caractérisée en ce que,
    la couche a été déposée sur un substrat par un procédé assisté par un plasma et que, sur la surface de la couche, des monomères M sont greffés sans action de plasma.
  14. Couche selon la revendication 13,
    caractérisée en ce que,
    le nombre n des monomères M, qui sont liés à un centre réactif de la surface de la couche, est supérieur à 1.
  15. Couche selon l'une ou l'autre des revendications 13 ou 14,
    caractérisée en ce que
    le monomère M est choisi parmi au moins un composé choisi parmi l'acide acrylique, l'acide méthacrylique et un dérivé de ces derniers.
  16. Couche selon la revendication 15,
    caractérisée en ce que,
    le dérivé est un ester, de préférence le méthacrylate de glycidyle.
  17. Couche selon l'une quelconque des revendications 13 à 17,
    caractérisée en ce que,
    le substrat est un métal ou une céramique.
  18. Couche selon l'une quelconque des revendications 13 à 17,
    caractérisée en ce que,
    le substrat est de l'acier, de l'acier galvanisé, de l'aluminium ou du magnésium.
  19. Couche selon l'une quelconque des revendications 13 à 18,
    caractérisée en ce que,
    la couche peut être obtenue par dépôt en plasma d'au moins un composé précurseur sur un substrat et fonctionnalisation sélective de la surface de la couche par greffage de monomères M sur des centres réactifs formés à la surface de la couche.
  20. Utilisation d'une couche selon l'une quelconque des revendications 13 à 19, pour la fixation adhérente et/ou résistante à la corrosion d'autres couches appliquées par la suite sur un substrat.
  21. Utilisation selon la revendication 20,
    caractérisée en ce que,
    la couche appliquée par la suite est une peinture, une masse adhésive, une encre d'imprimerie ou un apprêt.
EP00984979A 1999-11-08 2000-11-07 Couche a fonctionnalisation selective de la surface Expired - Lifetime EP1230042B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1999153667 DE19953667B4 (de) 1999-11-08 1999-11-08 Schicht mit selektiv funktionalisierter Oberfläche, Verfahren zur Herstellung sowie deren Verwendung
DE19953667 1999-11-08
PCT/EP2000/010983 WO2001034313A2 (fr) 1999-11-08 2000-11-07 Couche a fonctionnalisation selective de la surface

Publications (2)

Publication Number Publication Date
EP1230042A2 EP1230042A2 (fr) 2002-08-14
EP1230042B1 true EP1230042B1 (fr) 2003-08-13

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EP00984979A Expired - Lifetime EP1230042B1 (fr) 1999-11-08 2000-11-07 Couche a fonctionnalisation selective de la surface

Country Status (3)

Country Link
EP (1) EP1230042B1 (fr)
DE (1) DE19953667B4 (fr)
WO (1) WO2001034313A2 (fr)

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Publication number Priority date Publication date Assignee Title
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CN103889138B (zh) * 2012-12-24 2016-06-29 中国科学院微电子研究所 等离子体放电装置

Also Published As

Publication number Publication date
DE19953667B4 (de) 2009-06-04
WO2001034313A3 (fr) 2002-01-10
WO2001034313A2 (fr) 2001-05-17
EP1230042A2 (fr) 2002-08-14
DE19953667A1 (de) 2001-05-17

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