EP1051266B1 - Revetement polaire du type polymere - Google Patents

Revetement polaire du type polymere Download PDF

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Publication number
EP1051266B1
EP1051266B1 EP99901558A EP99901558A EP1051266B1 EP 1051266 B1 EP1051266 B1 EP 1051266B1 EP 99901558 A EP99901558 A EP 99901558A EP 99901558 A EP99901558 A EP 99901558A EP 1051266 B1 EP1051266 B1 EP 1051266B1
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EP
European Patent Office
Prior art keywords
process according
gas
coating
substrate
coated
Prior art date
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Revoked
Application number
EP99901558A
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German (de)
English (en)
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EP1051266A1 (fr
Inventor
Eva Maria Moser
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Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
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Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
EMPA
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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 present invention relates to a method for polar coating of Substrates using plasma polymerization.
  • the invention further relates to a coating of a polymeric substrate produced by the method and applications of the method.
  • the coating of polymeric substrates takes place, among other things, to the surface quality or To influence the appearance of the polymer or to mechanically, to protect physically as well as chemically. Be this to liability on the surface or to increase the printability, the surface prepare for further functional coatings, protection against abrasion or to ensure damage, the permeability of certain gases or liquids on or through the surface of the substrate reduce or prevent, or to the chemical resistance of the Increase substrates over certain chemicals.
  • the substrate or the increase in printability are the two named Procedures of importance.
  • corona discharge has shown that the printability of, for example, polymer packaging films only immediately after the treatment is good and after a few Hours to days the printability decreases again.
  • JP, A1 59-15569 and WO, A1 AU89 / 00220 proposed by means of plasma polymerization of an organic compound, together with possibly a working gas as well as water or water vapor to coat polymeric substrate. It is further proposed in WO95 / 04609 the surface by means of plasma polymerization of an organic compound to treat or coat in the presence of hydrogen peroxide.
  • US, A 3397132 relates to a coating of metallic surfaces, in the presence of organic gases and an inert carrier gas an electrical discharge takes place.
  • the inorganic gases neither mentioned the absence of water, otherwise stated essential.
  • other parameters such as pressure, temperature, concentration, voltage and frequency made precise statements. Through appropriate modifications the parameters are the desired improvements of the metallic Surfaces achieved by means of plasma coating.
  • A1 3908418 at least an organic compound and an optional inorganic gas are used.
  • Plastic containers are made impermeable to organic solvents Layers coated on the inside, with the inside of the container is charged with a low pressure plasma. In this process too water freedom is not an issue.
  • the hydrocarbon compounds which have up to a maximum of eight carbon atoms have, therefore, are relatively low molecular weight, whereby the compounds have a relatively high vapor pressure at room temperature.
  • Alkanes, alkenes, alkynes (acetylene), polyenes, one or more are preferably used polyhydric alcohols, carboxylic acids, ethers, aldehydes and / or ketones. These can be aliphatic, cycloaliphatic or aromatic hydrocarbon compounds act.
  • the use of water vapor as a process gas in a gas discharge is anything but ideal and must be avoided according to the invention. In the further a hydrated layer would become a deeper chemical and thermal Have resistance, which affects the subsequent processing steps as well as the definition and stability of the layers would have a negative impact.
  • the plasma-polymerized layer according to the invention is therefore anhydrous and so compact that it is hydrophilic, but almost no water in the Processing.
  • the process gas used for plasma polymerization or working gas is water-free or steam-free.
  • the Absence of water or water vapor at least in the process gas can also be ensured in any case that in the working gas or gas mixture may not contain any peroxide compounds are, for example, when using water and Can form oxygen in the plasma chamber.
  • all known plasma processes are suitable, such as microwave discharge, high or Low frequency discharge, DC magnetron discharge, arc evaporation, the use of electron beam gun etc.
  • the method proposed according to the invention is suitable for the coating of all known polymers used today Substrates, for example for the production of packaging materials, such as polyethylene, polyamide, polypropylene, PMMA, PVC, polyester such as PETP, PBTP, polyimide, polycarbonate etc. etc.
  • the polar layer can then act as an adhesion promoter between these materials and other layers, such as corrosion protection layers, serve or enable the combination of different materials, such as metal / polymer etc.
  • said polymer substrate is provided with a polar polymer-like coating or with a plasma layer with high surface tension, in which coating polar groups are incorporated, such as hydroxyl, carboxyl, carbonyl groups (see FIGS. 2a and 2b) or NO x groups, as a result of which excellent adhesion for polar functional layers and / or polar materials can be achieved on the surface of this coating, which is expressed, for example, in very good printability.
  • coating polar groups such as hydroxyl, carboxyl, carbonyl groups (see FIGS. 2a and 2b) or NO x groups
  • coating polar groups such as hydroxyl, carboxyl, carbonyl groups (see FIGS. 2a and 2b) or NO x groups
  • the one to be coated for example flexible substrate, such as a film, a hollow body or the like is placed in a vacuum chamber in which is the working gas, consisting of the components mentioned, is introduced. It is essential, as already mentioned above, that this working gas is free of water, steam or moisture is. Then a plasma-polymerized layer on the surface of the to be coated Material deposited.
  • the coating thus produced by means of plasma polymerization has usually a layer thickness of a few nm, such as between 1 and 100, preferably 5 to 20 nm; she can also be a few ⁇ m.
  • a layer thickness of a few nm, such as between 1 and 100, preferably 5 to 20 nm; she can also be a few ⁇ m.
  • the layer thickness judges the layer thickness according to the requirements, whether in addition to Printability also a scratch protection or an anti-fog effect to be achieved, for which purpose the coating achieved according to the invention can also make a contribution.
  • the ratio between the inorganic gas component, such as oxygen, nitrogen, ammonia or carbon monoxide or carbon dioxide, and the organic compound depends on the properties of the coating Has.
  • the ratio can vary widely depending on which components the gas mixture or the working gas contains. Table 1 shows a few examples. additionally to the components mentioned can of course further components, such as, in particular, noble gases, such as, for example Argon, helium, etc. can be used.
  • Alkanes are particularly suitable as organic compounds a chain length up to about eight carbon atoms, such as Methane, ethane, propane etc. But also alkenes, such as Ethylene, propylene, etc. are suitable as organic compounds.
  • acetylene or compounds based on acetylene like the so-called alkynes.
  • Polyenes are also suitable, i.e. Hydrocarbons with several double bonds, again with up to about eight carbon atoms.
  • Alcohols such as methanol, ethanol, propanol are also suitable etc. as well as polyhydric alcohols such as ethylene glycol.
  • Mono- or polyvalent organic acids are also suitable, Ethers, aldehydes and ketones. It can be with the described Hydrocarbon compounds around aliphatic, cycloaliphatic or act on aromatic hydrocarbons, all of the above connections, of course may be substituted, such as by amino groups, Halogens, ammonia etc.
  • a plasma reactor is flooded with the process gas mixture until the desired process pressure is reached, for example 1.6 x 10 -2 mbar.
  • a microwave discharge (2.45 GHz) was then ignited, the process gases being supplied continuously.
  • a layer with a polar fraction of 41% and a surface tension of 50 mN / m was achieved with a gas mixture of 48 sccm (standard cubic cm per minute) CO 2 , 12 sccm CH 4 and 12 sccm Ar, with a microwave power of 62 watts (sample 10 / PET).
  • the substrate was a 12 ⁇ m thin PET film or a 20 ⁇ m thin polypropylene film (Sample 2 / BOPP), representative of polymer substrates.
  • An increase in the process pressure up to atmospheric pressure will lead to a higher deposition rate and is currently the status of the optimization of the coatings.
  • Table 1 also shows that the desired surface tension for the corresponding substrate can be achieved by varying the output and the process gas mixture. The comparison of the different gas mixtures in Table 1 shows that the gas mixture has a greater influence on the hydrophilicity than the variation of the power supplied to the plasma by 80 watts.
  • Table 1 shows the coatings which were produced between July and October 1997 and for which the surface tension was measured again in January 1999.
  • the chemical structure of the hydrophilic layers is in the accompanying figures 2a and 2b can be seen.
  • the area share 1 is 6.5%, the area share 3 8.9%, the share 5 20.1% and the area share 7 64.5%.
  • the total carbon share is 76.2% as well as that of oxygen 23.8%.
  • the ratio of carbon to oxygen is thus 76.2: 23.8.
  • the area share 1 is 15.4%, of area 3 2.6%, of area 5 20.0% and of area 7 61.9%.
  • the share C (1s) is 70.0% and the share O (1s) 30.0%.
  • test conditions described above serve only to the basic idea of the present To explain the invention in more detail.
  • the Coating any functional layer that is more polar Nature
  • printing laminating (gluing - adhesion to polar Glue) on such a polar surface for new ones
  • Pressure media and adhesives which are based on the solvent water based.
  • doping of the coating with inorganic Anions (nitrogen, fluorine, etc.) and inorganic cations (Metals and metal oxides). This allows also other properties, such as the electrical conductivity according to the shift for the product requirement become.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Organic Insulating Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal Substances (AREA)

Claims (20)

  1. Procédé de revêtement de substrats par un revêtement polaire par polymérisation par plasma,
       caractérisé en ce que
       le gaz de traitement utilisé pour fabriquer un revêtement stable à long terme est un gaz exempt d'eau qui contient au moins un composé hydrocarburé éventuellement substitué, à chaíne de carbone pouvant atteindre huit atomes, et un gaz inorganique.
  2. Procédé selon la revendication 1, caractérisé en ce que la teneur volumique du composé organique dans le mélange gazeux est de 5 à 90%.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le gaz inorganique est l'oxygène, un halogène, l'hydrogène, un gaz noble, le monoxyde de carbone, le dioxyde de carbone, l'azote et/ou un autre gaz contenant de l'azote.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé par l'utilisation d'un hydrocarbure aliphatique, cyclo-aliphatique et/ou aromatique.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que le composé organique est un polyène, un alcool à une ou plusieurs valences, un acide carbonique à une ou plusieurs valences, un éther, un aldéhyde et/ou une cétone.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le composé organique utilisé est:
    un alcane, comme le méthane, l'éthane, le propane, le butane, le pentane et/ou l'hexane,
    un alcène, comme l'éthylène, le butylène, le propylène et/ou l'isopropylène, ou
    un alcyne comme l'acétylène ou un dérivé de l'acétylène.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le composé organique utilisé est un composé hydrocarburé substitué fluor, azote ou souffre.
  8. Procédé selon la revendication 1, caractérisé en ce qu'un substrat est revêtu au moyen de deux à quatre gaz du groupe constitué par CO2, CH4, O2, C2H2, NH3 et Ar.
  9. Procédé selon la revendication 8, caractérisé en ce qu'un substrat est revêtu au moyen d'un gaz de traitement constitué de CO2, C2H2 et Ar, de préférence selon un rapport volumique de 4:1:1.
  10. Procédé selon la revendication 8, caractérisé en ce qu'un substrat est revêtu au moyen d'un gaz de traitement constitué de NH3, CO2, CH4 et Ar, de préférence selon un rapport volumique de 2:1:1:1 ou 2:2:1:1.
  11. Procédé selon la revendication 8, caractérisé en ce qu'un substrat est revêtu à l'aide d'un gaz de traitement constitué de CO2 et CH4, de préférence selon un rapport volumique de 2:1 ou 4:1.
  12. Procédé selon la revendication 8, caractérisé en ce qu'un substrat est revêtu au moyen d'un gaz de traitement constitué de CO2, CH4 et Ar, de préférence selon un rapport volumique de 3:3:1 ou 4:1:1.
  13. Procédé selon la revendication 8, caractérisé en ce qu'un substrat est revêtu au moyen d'un gaz de traitement constitué de CO2 et AR, de préférence selon un rapport volumique de 4:1.
  14. Procédé selon la revendication 8, caractérisé en ce qu'un substrat est revêtu au moyen d'un gaz de traitement constitué de CH4, O2 et Ar, de préférence selon un rapport volumique de 1:1:1.
  15. Procédé selon la revendication 8, caractérisé en ce qu'un substrat est revêtu au moyen d'un gaz de traitement constitué de CO2, CH4, O2 et Ar, de préférence selon un rapport volumique de 1:2:1:2 ou 1:4:1:2.
  16. Procédé selon la revendication 8, caractérisé en ce qu'un substrat est revêtu au moyen d'un gaz de traitement constitué de CH4, NH3 et Ar, de préférence selon un rapport volumique de 2:2:1, 1:4:1 ou 1:2:1.
  17. Revêtement polymère d'un substrat, fabriqué selon un procédé conforme à l'une quelconque des revendications 1 à 7, caractérisé en ce que le revêtement polaire présente une tension superficielle initiale ≥ 45 mN/m qui reste approximativement inchangée pendant au moins un an.
  18. Utilisation du procédé selon l'une quelconque des revendications 1 à 16 pour revêtir des substrats polymères renforcés par des fibres céramiques, des fibres de verre, des fibres polymères, et/ou des fibres de carbone ou pour revêtir des substrats pulvérulents ou granuleux pour la fabrication d'un film polaire ou d'un corps de forme polaire.
  19. Utilisation du procédé selon l'une quelconque des revendications 1 à 16 pour revêtir des matières d'emballage, en particulier des feuilles, des bouteilles et autres récipients, et pour revêtir des substrats pour le collage de matières composites.
  20. Utilisation du procédé selon l'une quelconque des revendications 1 à 16 pour revêtir des substrats céramiques ou métalliques.
EP99901558A 1998-02-05 1999-02-05 Revetement polaire du type polymere Revoked EP1051266B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH28198 1998-02-05
CH28198 1998-02-05
PCT/CH1999/000050 WO1999039842A1 (fr) 1998-02-05 1999-02-05 Revetement polaire du type polymere

Publications (2)

Publication Number Publication Date
EP1051266A1 EP1051266A1 (fr) 2000-11-15
EP1051266B1 true EP1051266B1 (fr) 2003-03-12

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ID=4183425

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EP99901558A Revoked EP1051266B1 (fr) 1998-02-05 1999-02-05 Revetement polaire du type polymere

Country Status (9)

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US (1) US6746721B1 (fr)
EP (1) EP1051266B1 (fr)
JP (1) JP2002502688A (fr)
AT (1) ATE234165T1 (fr)
AU (1) AU2147299A (fr)
BR (1) BR9907692A (fr)
CA (1) CA2318129A1 (fr)
DE (1) DE59904532D1 (fr)
WO (1) WO1999039842A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU6051199A (en) * 1998-09-21 2000-04-10 Procter & Gamble Company, The Durably wettable, liquid pervious webs
TR200400076T4 (tr) * 2000-10-04 2004-02-23 Dow Corning Ireland Limited Bir kılıf oluşturmaya yarayan metot ve aparat
CH695222A5 (de) 2001-04-25 2006-01-31 Eva Maria Moser Gasdichter Behälter.
JP2003221456A (ja) * 2002-01-29 2003-08-05 Japan Gore Tex Inc 高接着性液晶ポリマーフィルム
GB0208261D0 (en) * 2002-04-10 2002-05-22 Dow Corning An atmospheric pressure plasma assembly
TW200308187A (en) * 2002-04-10 2003-12-16 Dow Corning Ireland Ltd An atmospheric pressure plasma assembly
TW200409669A (en) * 2002-04-10 2004-06-16 Dow Corning Ireland Ltd Protective coating composition
DE50311232D1 (de) * 2002-12-17 2009-04-09 Wipf Ag Substrat mit einer polaren plasmapolymerisierten schicht
GB0323295D0 (en) * 2003-10-04 2003-11-05 Dow Corning Deposition of thin films
MX2007005123A (es) * 2004-10-29 2007-06-25 Dow Global Technologies Inc Revestimientos resistentes a la abrasion a traves de deposicion de vapor quimica mejorada de plasma.
US20090142514A1 (en) * 2004-11-05 2009-06-04 Dow Corning Ireland Ltd. Plasma System
GB0509648D0 (en) * 2005-05-12 2005-06-15 Dow Corning Ireland Ltd Plasma system to deposit adhesion primer layers
US7910502B1 (en) * 2006-03-31 2011-03-22 Honeywell International Inc. Liquid submersion ballistic performance through hybridization
TWI424980B (zh) * 2008-02-04 2014-02-01 Nat Univ Tsing Hua 利用電漿技術將二氧化碳轉化為有用之有機產物

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US3397132A (en) 1964-10-16 1968-08-13 Du Pont Treatment of metal surfaces
US4312575A (en) * 1979-09-18 1982-01-26 Peyman Gholam A Soft corneal contact lens with tightly cross-linked polymer coating and method of making same
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FR2670495B1 (fr) 1990-12-14 1995-01-27 Elf Aquitaine Procede pour deposer un film mince antistatique a la surface d'un objet faconne, dont au moins la partie superficielle est en un polymere ou copolymere de styrene, et conferer ainsi audit objet un antistatisme durable.
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US5700559A (en) 1994-12-16 1997-12-23 Advanced Surface Technology Durable hydrophilic surface coatings
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Also Published As

Publication number Publication date
ATE234165T1 (de) 2003-03-15
US6746721B1 (en) 2004-06-08
BR9907692A (pt) 2000-11-14
CA2318129A1 (fr) 1999-08-12
DE59904532D1 (de) 2003-04-17
WO1999039842A1 (fr) 1999-08-12
JP2002502688A (ja) 2002-01-29
AU2147299A (en) 1999-08-23
EP1051266A1 (fr) 2000-11-15

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