Classifications

• • 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
• • 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
  • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
  • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12431—Foil or filament smaller than 6 mils
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31—Surface property or characteristic of web, sheet or block
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]

Definitions

• the present invention relates to sheet-like materials, in particular polymers or metallic foils using an atmospheric plasma are treated.
• finishing steps such as printing, coating, painting, Gluing, etc.
• plastic and metal foils if one sufficient wettability with solvent or water-based printing inks, Lacquers, primers, adhesives, etc. is given. In general, therefore, in or Corona treatment performed offline with the film processing.
• corona treatment has significant disadvantages. So it happens especially at higher ones Orbital velocities to a parasitic backside corona discharge if the sheet-like materials do not rest on the roller-shaped electrode. Furthermore, the corona treatment leads to a clear one electrostatic charge of the sheet-like materials that are winding the Materials difficult, the subsequent processing steps, such as painting, Printing or gluing hindered and especially in the manufacture of Packaging film is responsible for powdery materials such as Stick coffee or spices to the film and, in the worst case, leak Seal seams contribute. After all, corona treatment is always one Filament discharge that does not produce a homogeneously closed surface effect. It is also found over time that there is a loss of surface properties occurs due to the migration of film additives and aqueous a molecular Rearrangement based on minimizing surface energy takes place.
• corona treatment is limited to thin substrates such as Plastic films and papers. For thicker materials, the total resistance is too large between the electrodes to ignite the discharge. But then it can individual punctures also occur. Corona discharge should not be used for electrically conductive plastics. They also show dielectric Electrodes in metallic or metal-containing webs are often limited Effect. The dielectrics can easily due to the permanent stress run away. This is particularly the case with silicone-coated electrodes. Ceramic electrodes are very resistant to mechanical stress sensitive.
• surface treatments can also be caused by flames or light can be performed.
• the flame treatment is usually at Temperatures around 1700 ° C and intervals between 5 and 150 mm.
• the foils heat up briefly to high temperatures of around 140 ° C, effective cooling must be carried out.
• the treatment results are good compared to the chill roll be brought to an electrical potential that the ions of the flame towards treating web accelerates (polarized flame).
• a treatment intensity that is too low leads to minor, insufficient, effects. Too strong intensities lead to one Melting of the surfaces, the functional groups submerge inwards and are therefore inaccessible.
• the main disadvantage of the corona treatment the localized micro-discharges (Filaments) can be avoided by using a low pressure plasma become. These mostly “cold" plasmas are by means of equal, alternating or High frequency current or generated by microwaves. With only low thermal Loading of the - usually sensitive - material to be treated energetic and chemically active particles provided. These cause one targeted chemical reaction with the material surface, since the processes are in the gas phase at low pressure in a particularly effective manner and the Represents discharge as a homogeneous space discharge cloud. With microwave excitations whole reactor vessels can be used in the Giga-Hz range Fill in the plasma discharge. Compared to wet chemical processes are extreme small amounts of process agents are necessary.
• SiOx-based layers made of organosilicon Compounds such as tetramethylsilane (TMS), tetarethoxysilane (TEOS) or hexamethyldisiloxane (HMDSO), polymer-like hydrocarbon layers Hydrocarbons such as methane, acetylene or propargyl alcohol as well as fluorinated Carbon layers from fluorinated hydrocarbons such as Tetrafluoroethene.
• TMS tetramethylsilane
• TEOS tetarethoxysilane
• HMDSO hexamethyldisiloxane
• Hydrocarbons such as methane, acetylene or propargyl alcohol as well as fluorinated Carbon layers from fluorinated hydrocarbons such as Tetrafluoroethene.
• DE 29805999 U1 describes a device for the plasma treatment of surfaces described, which is characterized by a rotary head, the at least one Eccentrically arranged plasma nozzle for generating a parallel to the axis of rotation directed plasma beam. If the workpiece is relatively high Speed rotating rotating head is moved, the plasma jet sweeps a strip-like surface zone of the workpiece, the width of which corresponds to the diameter corresponds to the circle described by the plasma nozzle during rotation. In this way it is possible with a comparatively small apparatus A relatively large surface can be rationally pretreated. Yet the surface dimensions do not correspond to those, as usually with the Processing of film materials on an industrial scale.
• corona nozzles for the indirect treatment of workpiece surfaces is described.
• Corona nozzles oscillate or rotate between the electrodes guided air flow, so that you get a flat discharge zone in which the Surface of the workpiece to be treated with the corona discharge tufts can be painted over.
• the disadvantage of this process was that aqueous mechanical to equalize the electrical discharge Moving component must be provided, which has a high constructive Effort required.
• the cited documents also do not describe in what maximum widths such corona nozzles are manufactured and used can be.
• the object was plastic and metal foils To be made available, which are processed or modified homogeneously, so that subsequent finishing steps, such as printing, coating, Painting, gluing, etc. without wetting problems and with good ones Have adhesive properties carried out.
• the aim was to use a method that the through Low-pressure plasmas (batch operation, costs), corona (filament-shaped discharge, Backside treatment, electrostatic charging, etc.) and plasma nozzles (strip-like surface treatment) given disadvantages.
• this is achieved by treating the entire or part of the surface homogeneously sheet-like metallic materials with a thickness of less than 100 ⁇ m or sheet-like polymeric materials which are obtained by passing through an indirect plasmatron generates atmospheric plasma on the surface of the Material can act.
• An indirect plasmation suitable for the method according to the invention is e.g. described in EP-A-851 720 (incorporated by reference).
• the burner is characterized by two coaxially spaced apart Electrodes. A direct current arc burns between these, through an cascaded arrangement of freely adjustable length is wall stabilized. Through a Blowing transversely to the arc axis can be a band-shaped, laterally flowing Exit the plasma jet.
• This burner also called plasma broad-beam burner, is also characterized in that a magnetic field exerts a force on the arc that is exerted by the flow of the plasma gas on the arc Counteracts force.
• the burner can also be of various types Plasma gases are supplied.
• At least one neutrode with a permanent magnet pair to influence the shape and position of the plasma arc. Due to the number, placement and field strength of the magnets used, you can Operating parameters such as gas volume and gas speed be taken. Furthermore, at least individual neutrodes with one Possibility of supplying a gas to the plasma chamber, e.g. a channel be provided. This allows this plasma gas to target the arc in a particularly targeted manner and fed homogeneously. By blowing transversely to the arc axis a band-shaped plasma free jet flowing out to the side can emerge. Through the Applying a magnetic field becomes a deflection and the resulting one Preventing the arc from breaking.
• the sheet-like materials described according to the invention can be used both in Connection to a film production as well as before further processing, i.e. before the Treat printing, laminating, coating, etc. of foils.
• the thickness of the polymeric film materials is essentially irrelevant and moves in the thickness range of 0.5 ⁇ m and 2 cm, preferably in the range between 10 and 200 ⁇ m.
• the materials described according to the invention can be polymeric materials, but also metallic substrates, in particular also plastic and metal foils.
• the materials according to the invention also include polymeric sheet materials, which are optionally vapor-coated with metal, metal oxides or SiO x .
• plastic films are understood in particular to be those which consist of a thermoplastic material, in particular of polyolefins such as polyethylene (PE) or polypropylene (PP), of polyester such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) or liquid-crystalline polyesters (LCP) , made of polyamides such as nylon 6,6; 4.6; 6; 6.10; 11; 12;
• PVC polyvinyl chloride
• PVDC polyvinyl dichloride
• PC polycarbonate
• PVOH polyvinyl alcohol
• EVOH polyacrylonitrile
• PAN polyacrylonitrile
• ABS polyacrylic butadiene styrene
• ABS polystyrene-acrylonitrile
• ASA polyacrylic ester-styrene-acrylonitrile
• PS made of polyacrylates
• Plastic films are also understood to mean those which consist of a thermoplastic material and with a metal of the 3rd main group or the 1st or 2nd subgroup or with SiO x or a metal oxide of the 2nd or 3rd main group or the 1st or 2nd subgroup are steamed.
• Metal foils are understood to be foils made of aluminum, copper, gold, Silver, iron (steel) or alloys of the metals mentioned.
• sheet-like materials according to the invention include such understood, which are so surface-treated by an atmospheric plasma, that by interacting with the plasma gas, an increase in surface tension the polymer surface takes place.
• plasma gas and / or aerosol a plasma graft or a Plasma coating (plasma polymerization) on or on the surface be performed.
• the extremely reactive species of plasma gas can do this have a cleaning and even disinfectant effect on the surface.
• Web-like materials according to the invention which are polarized, thus receive an increase in surface tension. This will ensure complete wetting with polar liquids such as alcohols or water.
• the Polarization occurs when atoms or molecular fragments - excited by the Plasma - react with surface molecules and consequently into the surface to be built in. Since these are mostly fragments containing oxygen or nitrogen, also speaks of surface oxidation.
• Sheet-like materials according to the invention are provided with a surface graft provided if a targeted incorporation of molecules, preferably by a reaction on the polymer surface.
• a surface graft provided if a targeted incorporation of molecules, preferably by a reaction on the polymer surface.
• molecules preferably by a reaction on the polymer surface.
• carbon dioxide reacts with hydrocarbon compounds to form carboxyl groups.
• Web-like materials according to the invention with a plasma coating are characterized in that a reactive plasma gas by a kind of polymerization is deposited more or less closed on the surface. That’s it among other things possible release, barrier, antifog or in general To create protective layers on the plastic and metal foils.
• Web-like materials according to the invention, for surface cleaning are characterized by being on the surface deposited impurities, additives or low molecular weight components are oxidized and be vaporized. Disinfection occurs when the number of germs in the Kind is reduced, watery it lies below the critical germ concentration.
• the plasma gas for the treatment of the web-shaped according to the invention Materials is used, is characterized in that it is made of Mixtures of reactive and inert gases and / or aerosols. Through the high energy in the arc leads to excitation, ionization, fragmentation or radical formation of the reactive gas and / or aerosols. Due to the Flow direction of the plasma gas are the active species from the Burner chamber carried out and can be used to interact with the Surface of plastic and metal foils are brought.
• the oxidizing process gas and / or aerosol can be used in concentrations of 0 to 100%, preferably between 5 and 95%.
• Oxygen-containing gases and / or aerosols such as oxygen (O 2 ), carbon dioxide (CO 2 ), carbon monoxide (CO), ozone (O 3 ), hydrogen peroxide gas (H 2 O 2 ), water vapor are preferably used as oxidizing plasma gases and / or aerosols (H 2 O), evaporated methanol (CH 3 OH), nitrogen-containing gases and / or aerosols such as nitrous gases (NO x ), nitrous oxide (N 2 O), nitrogen (N 2 ), ammonia (NH 3 ), hydrazine (H 2 N 4 ), sulfur-containing gases and / or aerosols such as sulfur dioxide (SO 2 ), sulfur trioxide (SO 3 ), fluorine-containing gases and / or aerosols such as terafluorocarbon (CF 4 ), sulfur hexafluoride (SF 6 ), xenon difluoride (XEF 2 ), nitrogen trifluoride (NF 3 ), boron trifluoride (BF 3 ),
• Crosslinkable plasma gases and / or aerosols are preferably unsaturated hydrocarbons such as ethylene, propylene, butene, acetylene; saturated hydrocarbons with the general composition C n H 2n + 2 , such as methane, ethane, propane, butane, pentane, iso-propane, iso-butane; Vinyl compounds such as vinyl acetate, methyl vinyl ether; Acrylates such as acrylic acid, methacrylic acid, methyl methacrylate; Silanes with the general composition Si n H 2n + 2 , halogenated silicon hydrides such as SiCl 4 , SiCl 3 H, SiCl 2 H 2 , SiClH 3 , alkoxysilanes such as teraethoxysilane; Hexamethyldisilazane; Hexamethyldisiloxane used.
• unsaturated hydrocarbons such as ethylene, propylene, butene, acetylene
• Maleic anhydride, acrylic acid compounds, vinyl compounds, carbon dioxide (CO 2 ) are preferably used as graftable process gases and / or aerosols.
• the active and the inert gas and / or aerosol is preferably used in a preliminary stage mixed and then introduced into the zone of the arc discharge.
• certain gas and / or aerosol mixtures such as, for example Oxygen and silanes immediately before introduction into the zone of the Arc discharge mixed.
• Plasmas are characterized in that their temperatures are in the range of Arc at several 10,000 Kelvin. Because the escaping plasma gas is still Having temperatures in the range of 1000 to 2000 Kelvin is sufficient Cooling of the temperature-sensitive polymeric materials necessary. This can generally done by an effectively working chill roll.
• the contact time of plasma gas and foil material is very important. This should preferably be reduced to a minimum so that a thermal No damage to the materials. A minimal contact time is always through reached an increased web speed.
• the web speeds of the foils is usually higher than 1 m per minute, it is preferably between 20 and 600 m per minute.
• the plastic and metal foils in very little Pass the distance past the burner opening (nozzle). This is preferably done at a distance of 0 to 40 mm, particularly preferably at a distance of 1 to 15 mm.
• Plastic and metal foils according to the invention succeeded in the atmospheric Plasma by using the described plasma broad-beam burner to produce treated surfaces. This was achieved with a - compared to other processes - only a small outlay on equipment, and at the same time low Litigation costs. Since in the example each neutrode of the plasma torch has an outlet opening for the plasma gas, this can target the arc and be fed homogeneously. The laterally flowing, band-shaped plasma free jet therefore leads to a particularly homogeneous processing of the surface.
• the relevant properties of the following film samples were as follows measured.
• the thermal damage to the film sections was visual or by Microscopic examinations assessed.
• the determination of the surface tension was carried out with commercially available test inks from Arcotec fatiguentechnik GmbH according to DIN 53364 or ASTM D 2587.
• the specification of the surface tension was done in mN / m.
• the measurements were carried out immediately after treatment. The measurement errors are ⁇ 2 mN / m.
• the element distribution on the film surface was determined by means of ESCA measurements (Photoelectron spectroscopy). The specification of the element distribution was done in percent.
• PE 1 No. 4 to 7, Table 1
• the materials listed in Table 1 were also pretreated by means of corona discharge and tested for their surface tension with test inks immediately after the treatment.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Plasma & Fusion (AREA)
• Physics & Mathematics (AREA)
• Treatments Of Macromolecular Shaped Articles (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)
• Manufacturing Of Magnetic Record Carriers (AREA)
• Printing Methods (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)

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• 2000
  • 2000-03-08 DE DE2000111274 patent/DE10011274A1/de not_active Withdrawn
• 2001
  • 2001-02-23 EP EP20010103655 patent/EP1132492A3/fr not_active Withdrawn
  • 2001-02-26 MX MXPA01002048A patent/MXPA01002048A/es not_active Application Discontinuation
  • 2001-03-01 JP JP2001056823A patent/JP2001329083A/ja active Pending
  • 2001-03-06 PL PL34629001A patent/PL346290A1/xx not_active Application Discontinuation
  • 2001-03-06 US US09/800,370 patent/US20020018897A1/en not_active Abandoned
  • 2001-03-06 CA CA 2339675 patent/CA2339675A1/fr not_active Abandoned
  • 2001-03-07 NO NO20011153A patent/NO20011153L/no unknown
  • 2001-03-07 RU RU2001106186/02A patent/RU2001106186A/ru not_active Application Discontinuation
  • 2001-03-08 BR BR0100936A patent/BR0100936A/pt not_active Application Discontinuation

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