EP1272286B1 - Verfahren zum abscheiden einer polymerschicht - Google Patents
Verfahren zum abscheiden einer polymerschicht Download PDFInfo
- Publication number
- EP1272286B1 EP1272286B1 EP01927907A EP01927907A EP1272286B1 EP 1272286 B1 EP1272286 B1 EP 1272286B1 EP 01927907 A EP01927907 A EP 01927907A EP 01927907 A EP01927907 A EP 01927907A EP 1272286 B1 EP1272286 B1 EP 1272286B1
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- EP
- European Patent Office
- Prior art keywords
- process according
- group
- deposited
- discharge
- polymer coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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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
- B05D1/62—Plasma-deposition of organic layers
Definitions
- the invention relates to a method for deposition a polymer layer on a substrate after the Preamble of claim 1, and the use of thus coated substrate according to claims 11 to 17.
- the layer deposition process according to the invention can use plasma polymer coated substrates with a very high density of functional groups are provided, which as reactive anchor groups for subsequent coatings or chemical Serve reactions. So the functional groups the surface itself is either hydrophilic or hydrophobic or they can go into chemical reactions which to form such a hydrophilic or lead hydrophobic surface. Furthermore, by the functional groups the adsorption behavior against a variety of substances, such as Example metal ions, organic substances, biomolecules etc. can be modified and an adherent Connection of the same can be realized.
- the procedure is preferably used with such substrates that inherently have relatively inert surfaces, i.e. are chemically inert, as is the case with common Polymers such as polyolefins or fluorinated polymers in general is the case.
- the polymer surface provided with very reactive radical centers growing up a polymer chain This can one prepared the previously in a first variant Surface directly with polymerizable organic Bring connections in contact.
- the organic Compounds are in liquid or gaseous form Status.
- the prepared one Surface in contact with moist air first brought so that peroxides or hydroperoxides form, which then thermally or photochemically dissociate to form reactive oxide radicals can and, in contact with a suitable organic Connection, also the growth of a polymer chain cause.
- plasma polymerization starting from gaseous organic compound that possess the desired functional group, by Excitation and dissociation in a plasma reactive Species formed.
- the reactive species condense on the surface and form a more or less highly covalently cross-linked layer.
- at appropriate litigation can be achieved that a Part of the functional groups remains intact.
- Those remaining in the deposited layer functional groups can be identified by physical Processes such as infrared spectroscopy, proven, see J.P.S. Baydal, "Controlled plasma chemical deposition of polymer Coatings ", IEEE Seminar Plasma Polymerization for the Future, IEEE, London, 1999, 2/1.
- Plasma polymerization processes usually work with low pressure plasmas and therefore require use elaborate vacuum equipment. You are relative expensive, and especially for the treatment of Low-price products, such as packaging films, not economical.
- the invention is based on the technical problem a method of depositing a polymer layer underneath Use of a filamented gas discharge To provide atmospheric pressure, which has the disadvantages largely avoided according to the prior art.
- the method is also intended to use plasma polymer-coated substrates, in particular plasma polymer-coated polymers, provide that have a very high density of functional Have groups.
- Filamented gas discharges for example filamented barrier discharges
- filaments have a statistical distribution of transient micro-discharges, the so-called filaments.
- current densities 100 to 1000 A / cm 2 in the filaments with very high electron densities of 10 14 to 10 15 cm -3 .
- functional groups of the introduced organic compound are completely, or at least to a very considerable extent, destroyed upon contact with the high-energy particles of the gas discharge.
- This applies in particular to the quite fragile functional groups such as the epoxy, the carboxyl, or the primary, secondary or tertiary amino group.
- destroyed functional groups are no longer formed to any appreciable extent under plasma conditions and are therefore replaced again, which applies in particular to the epoxy group.
- the process can be operated at or near atmospheric pressure, ie in the range from approx. 0.2 bar to 2 bar, ie from 2x10 4 Pa to approx. 2x10 5 Pa. It is therefore advantageously possible to dispense with the use of complex and expensive vacuum systems.
- the substrates to be coated are inert Suitable polymer surfaces, for example Polyethylene, polypropylene or high-performance plastics such as polyoxymethylene, polyether ketone or polypropylene sulfide.
- Noble gases are known to work under normal conditions are chemically inert. Can in the plasma-excited state however, they do trigger chemical reactions can lead to the destruction of functional groups.
- the filamented discharge can be by means of a Sinusoidal voltage can be excited.
- Sinusoidal voltage can be excited.
- the greatest possible density of functional groups on the polymer layer however, it turned out to be proven to be a pulsed sinusoidal voltage use. This will be explained below.
- the layer thickness also increased during t 2 , ie the coating rate was greater than zero. This indicates that intact and non-excited molecules react with the sufficiently stable radical centers on the surface in the sense of a classic radical polyaddition.
- the starting substance for the separation of the with Plasma polymer layer produced according to the method serve one or more, with functional Grouped, radically polymerizable Connection.
- the organic compound supplied to the discharge must be polymerizable or polymerizable Have group.
- a carbon double bond suitable such as those found in vinyl, allyl, Acrylic, or methacrylic compounds are present, since these according to previous understanding is split up and that concerned carbon atom with a covalent bond the radical.
- the organic compound also has a chemical functional group containing at least one of the elements Contains O, N, S, P or a halogen.
- Suitable nitrogen-containing groups are, for example primary, secondary and tertiary amino, nitrile and Nitro groups.
- Suitable sulfur-containing groups are, for example Thiol, mercapto, sulfonic acid, sulfone, sulfoxide or Thioether groups.
- the group is the phosphate group and the phosphoric acid ester group called.
- a particularly interesting halogen-containing group is the trifluoromethyl group, since this is sufficient Concentration or density on the surface of this one can impart very low surface tension.
- the epoxy group is suitable for layer deposition especially because they are slightly covalent Can form bonds to the subsequent layer.
- coated according to the invention Brought the substrate into contact with an adhesive partner, for Example of a paint job, so are the Epoxy groups especially if it is one Adhesive partner is based on epoxy. So is liable to Example, an epoxy-based varnish is particularly adhesive with such a coated substrate built-in epoxy groups.
- the choice of a polymerizable organic compound with at least one polar hydroxyl or Carboxyl group is particularly suitable when the Surface of the coated substrate is hydrophilic to be executed.
- Amino groups are advantageous if the Plasma polymer layer subsequently with an adhesive should be provided on an epoxy basis, since epoxy groups are very reactive towards amino groups. Furthermore can amino groups for example for the Use immobilization of proteins. To do this expressly on the publication of Y. Uyama, K. Kato and Y. Ikada, Advances in Polymer Science 137, p. 28, 1998. Furthermore, amino groups can also via a reaction with cyanuric chloride to couple Poly (ethylene) oxide chains, which in turn serve the Adhesion of proteins on the surface strong to reduce. In this regard, W.R. Gombotz et. al., J. Biomed. Mat. Res. 25, pp. 1547, 1991 directed.
- Plasma polymer layers are also bonds, and both such bonds in one additional adhesive is required as well such bonds in which the polymer layer even the adhesive effect develops (so-called AutoadPSsionsISSen).
- Other examples are Adhesive connections with printing inks to be applied or a metallic coating or Metallization.
- biocompatible layers are provided which are used for Example on implants for biomedical Applications are provided. So it can depend on Use case with these implants is desirable be that there are proteins, organic cells or Have cell cultures deposited, not separate let, or only special representatives of the same let it separate. For example, in the event that the implant is firmly anchored to the connective tissue should be desirable that the surface with functional groups are attached to the attachment support from cells. Furthermore, by the Loading with an antibiotic or Growth factor the surface additional functions fulfill.
- the specific relationships between Art the functional group on the surface on the one hand, and the liability of biological material such as proteins or cells, on the other hand, is described, for example, in C.-P. Klages, Mat.-wiss. u. Maschinenstofftech. 30, p. 767, 1999, described in detail so that in this regard is expressly referred to this article.
- An example is the covalent immobilization of Collagen called by carboxyl groups.
- the organic compound is introduced either gaseous or as an aerosol.
- a gaseous one Introducing is advisable when the vapor pressure is sufficiently high, for example with numerous Monomers.
- the carrier gas is used for this most of the time liquid organic compound passed.
- a contribution as an aerosol for high molecular weight compounds Low vapor pressure is an advantage, for many dimers or polymers. If it is introduced as an aerosol, see above usually a high coating rate realize.
- a filamented barrier discharge can be selected as the filamented gas discharge, cf. Fig. 1 and the embodiment.
- a barrier discharge is understood to be a gas discharge as described by H. Gobrecht et. al., "On Silent Discharge in Ozonizers", Ber. Bunsenges. 68, pp. 55-63, 1965.
- An electronically controlled arc discharge can also be selected. 2
- an electronically controlled high voltage U is applied to two high-voltage electrodes 6, 6 '.
- the activated gas particles generated in the arc discharge are transported to the substrate surface 8 to be coated with the aid of a strong gas stream 7.
- the activated gas particles constrict to form thin discharge channels 9, so that a filamented form of discharge is also present here.
- the advantage of this discharge arrangement is that the electrodes 6, 6 'themselves are coated significantly less than in the case of the filamented barrier discharge. This advantageously leads to a lower maintenance requirement of the arrangement, which enables economical work in continuous operation.
- an approximately 1 ⁇ m thick layer of a ten percent polymer solution of polyglycidyl methacrylate (abbreviated to Poly-GMA) in methyl ethyl ketone (MEK) is produced by immersing a silicon wafer in the solution of the polymer in butanone.
- Poly-GMA polyglycidyl methacrylate
- MEK methyl ethyl ketone
- an epoxide concentration of 7.0 mmol / g was determined by determining the absorption of the characteristic wave numbers of 850 cm -1 and 910 cm -1 of the epoxy group. It can be assumed to a good approximation that the polymer and the deposited layers have the same density in accordance with the method according to the invention. Furthermore, it can be assumed that the epoxy groups are almost completely retained when the layer is formed from the polymer solution.
- the electrodes are two ceramic-insulated rods 1, 1 'of 15 cm length which are arranged with their longitudinal axis parallel to the substrate surface.
- the viewing direction in Fig. 1 is the direction of these longitudinal axes.
- the distance between the electrodes 1, 1 'from the substrate 2 is 0.9 cm, the substrate table 3 being moved back and forth under the electrodes at a speed of 1 cm / s.
- the movement of the substrate table 3 is indicated by the horizontal double arrow below the substrate 2.
- the electrodes 1, 1 'are supplied by a high-voltage generator with sinusoidal alternating voltage U of 5 to 10 kV with the frequency f 38 kHz, the primary-side power being approximately 40 W.
- Nitrogen is passed through at a room temperature of 23 ° C a container with the liquid monomer glycidyl methacrylate (GMA) headed.
- GMA liquid monomer glycidyl methacrylate
- the one with the gaseous GMA loaded nitrogen with a gas flow of 10 l / min through the gas shower 4 between the electrodes 1 passed into the discharge zones 5, 5 'where the Substrate 2 was coated.
- Polymer films such as polyethylene and Polypropylene chosen.
- 5 'can thin layer of about 10 nm thickness can be produced.
- the thickness of the deposited layer can be increased accordingly.
- the layer deposition method according to the invention is good is suitable with plasma polymer coated substrates a large number of epoxy groups put.
- the Discharge with otherwise unchanged process parameters not with a continuous sine voltage, but operated with a pulsed sine voltage.
- the Pulse time was 1 ms at a pulse frequency of 20 Hz.
- the evaluation of the infrared spectra showed that the Concentration of the epoxy groups now 6.3 mmol / g scam. With the pulsed voltage one could far higher concentration of epoxy groups on the Surface of the substrate can be provided as with simple sine voltage. Apparently one survived far greater proportion of the organic compound introduced functional groups.
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Chemical Vapour Deposition (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Description
Claims (18)
- Verfahren zum Abscheiden einer Polymerschicht unter Einsatz einer filamentierten Gasentladung, bei der der Entladung ein Trägergas und eine organische Verbindung zugeführt werden, wobei die organische Verbindung polymerisierbar ist und sie eine Kohlenstoff-Doppelbindung und zusätzlich eine sauerstoff-, stickstoff-, schwefel-, oder phosphorhaltige funktionelle Gruppe oder eine Trifluormethylgruppe aufweist.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die sauerstoffhaltige funktionelle Gruppe eine Epoxid-, Ether-, Keto-, Aldehyd-, Carboxyl-, oder Hydroxylgruppe ist.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die stickstoffhaltige funktionelle Gruppe eine Amino-, Nitril-, oder Nitrogruppe ist.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die schwefelhaltige funktionelle Gruppe eine Thiol-, Mercapto-, Sulfonsäure-, Sulfon-, Sulfoxid- oder Thioethergruppe ist.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die phosphorhaltige Gruppe eine Phosphatgruppe oder eine Phosphorsäureesthergruppe ist.
- Verfahren nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass ein Gasdruck von 2x104 Pa bis 2x105 Pa gewählt wird.
- Verfahren nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die organische Verbindung gasförmig oder als Aerosol eingebracht wird.
- Verfahren nach mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Entladung gepulst betrieben wird.
- Verfahren nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass als Trägergas Stickstoff zugeführt wird.
- Verfahren nach mindestens einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Abscheidung unter Einsatz einer filamentierten Barrierenentladung erfolgt.
- Verfahren nach mindestens einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die Abscheidung unter Einsatz einer elektronisch gesteuerten Bogenentladung erfolgt.
- Verfahren zur Herstellung einer haftfesten Lackierung, insbesondere einer Lackierung auf Epoxidbasis, bei dem eine Polymerschicht mittels des Verfahrens nach einem der Ansprüche 1 bis 11 abgeschieden wird.
- Verfahren zur Verklebung, insbesondere für Verklebungen unter Einsatz von Klebmassen auf Epoxidbasis, bei dem eine Polymerschicht mittels des Verfahrens nach einem der Ansprüche 1 bis 11 abgeschieden wird.
- Verfahren zur Verklebung ohne zusätzliche Klebmasse, bei dem eine Polymerschicht mittels des Verfahrens nach einem der Ansprüche 1 bis 11 abgeschieden wird.
- Verfahren zum Aufbringen von Druckfarben, insbesondere von Druckfarben auf Wasserbasis, bei dem eine Polymerschicht mittels des Verfahrens nach einem der Ansprüche 1 bis 11 abgeschieden wird.
- Verfahren zur Herstellung einer Metallisierung, bei dem eine Polymerschicht mittels des Verfahrens nach einem der Ansprüche 1 bis 11 abgeschieden wird.
- Verfahren zur Herstellung einer biokompatiblen Schicht, insbesondere einer biokompatiblen Schicht auf Implantaten, bei dem eine Polymerschicht mittels des Verfahrens nach einem der Ansprüche 1 bis 11 abgeschieden wird.
- Verfahren zur Beeinflussung der Anlagerung von Proteinen und Zellen, bei dem eine Polymerschicht mittels des Verfahrens nach einem der Ansprüche 1 bis 11 abgeschieden wird.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10017846 | 2000-04-11 | ||
DE10017846A DE10017846C2 (de) | 2000-04-11 | 2000-04-11 | Verfahren zum Abscheiden einer Polymerschicht und Verwendung derselben |
PCT/EP2001/004108 WO2001076773A2 (de) | 2000-04-11 | 2001-04-10 | Verfahren zum abscheiden einer polymerschicht und verwendung derselben |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1272286A2 EP1272286A2 (de) | 2003-01-08 |
EP1272286B1 true EP1272286B1 (de) | 2004-03-17 |
Family
ID=7638274
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01927907A Expired - Lifetime EP1272286B1 (de) | 2000-04-11 | 2001-04-10 | Verfahren zum abscheiden einer polymerschicht |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1272286B1 (de) |
AT (1) | ATE261781T1 (de) |
DE (2) | DE10017846C2 (de) |
WO (1) | WO2001076773A2 (de) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TR200400076T4 (tr) | 2000-10-04 | 2004-02-23 | Dow Corning Ireland Limited | Bir kılıf oluşturmaya yarayan metot ve aparat |
TW200409669A (en) | 2002-04-10 | 2004-06-16 | Dow Corning Ireland Ltd | Protective coating composition |
DE10248085A1 (de) * | 2002-10-15 | 2004-05-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Plasmapolymere Haftschichten |
US20060068224A1 (en) * | 2004-09-30 | 2006-03-30 | George Grobe | Coated biomedical device and associated method |
GB0507612D0 (en) | 2005-04-15 | 2005-05-25 | Univ Durham | A method for producing a thiol functionalised surface |
GB0509648D0 (en) | 2005-05-12 | 2005-06-15 | Dow Corning Ireland Ltd | Plasma system to deposit adhesion primer layers |
DE102007006786B4 (de) | 2006-02-22 | 2022-02-10 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Anlage und Verfahren zum Beschichten eines Substrates |
DE102010049807A1 (de) | 2010-10-27 | 2012-05-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Immobilisierung mindestens einer Substanz auf Oberflächen |
DE102010044114A1 (de) | 2010-11-18 | 2012-05-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zum Verbinden von Substraten und damit erhältliche Verbundstruktur |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE604952A (de) * | 1960-06-15 | 1961-12-13 | ||
US3443980A (en) * | 1966-04-15 | 1969-05-13 | Du Pont | Process of producing laminar film structures |
DE3827630A1 (de) * | 1988-08-16 | 1990-02-22 | Hoechst Ag | Flaechengebilde aus einem substrat und einem ueberzug und verfahren zu seiner herstellung |
US5326584A (en) * | 1989-04-24 | 1994-07-05 | Drexel University | Biocompatible, surface modified materials and method of making the same |
US6342275B1 (en) * | 1993-12-24 | 2002-01-29 | Seiko Epson Corporation | Method and apparatus for atmospheric pressure plasma surface treatment, method of manufacturing semiconductor device, and method of manufacturing ink jet printing head |
DE19611936C2 (de) * | 1996-03-27 | 2003-02-13 | Leica Microsystems | Verfahren zur Erzeugung einer haftfesten Beschichtung mit optischen und/oder mechanischen Funktionen auf einer Polymethylmetacrylat-Substratoberfläche |
DE19802740A1 (de) * | 1998-01-26 | 1999-07-29 | Leybold Systems Gmbh | Verfahren zur Behandlung von Oberflächen von Substraten aus Kunststoff |
DE19953667B4 (de) * | 1999-11-08 | 2009-06-04 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Schicht mit selektiv funktionalisierter Oberfläche, Verfahren zur Herstellung sowie deren Verwendung |
-
2000
- 2000-04-11 DE DE10017846A patent/DE10017846C2/de not_active Expired - Fee Related
-
2001
- 2001-04-10 DE DE50101710T patent/DE50101710D1/de not_active Expired - Lifetime
- 2001-04-10 AT AT01927907T patent/ATE261781T1/de not_active IP Right Cessation
- 2001-04-10 WO PCT/EP2001/004108 patent/WO2001076773A2/de active IP Right Grant
- 2001-04-10 EP EP01927907A patent/EP1272286B1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE10017846C2 (de) | 2002-03-14 |
EP1272286A2 (de) | 2003-01-08 |
WO2001076773A2 (de) | 2001-10-18 |
DE50101710D1 (de) | 2004-04-22 |
DE10017846A1 (de) | 2001-10-25 |
WO2001076773A3 (de) | 2002-02-28 |
ATE261781T1 (de) | 2004-04-15 |
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