# Patent

## Title
Atmospheric glow discharge with concurrent coating deposition

## Abstract

A plasma is produced in a treatment space by diffusing a plasma gas at atmospheric pressure and subjecting it to an electric field created by two metallic electrodes separated by a dielectric material, a precursor material is mixed with the plasma, and a substrate film or web is coated by vapor deposition of the vaporized substance at atmospheric pressure in the plasma field. The deposited precursor is cured by electron-beam, infrared-light, visible-light, or ultraviolet-light radiation, as most appropriate for the particular material being-deposited. Plasma pre-treatment and post-treatment steps are used to enhance the properties of the resulting coated products. Similar results are obtained by atomizing and spraying the liquid precursor in the plasma field.

## Background
RELATED APPLICATIONS
This application is a continuation-in-part of U.S. Ser. No. 10/228,358, filed on Aug. 26, 2002, which is a continuation-in-part of Ser. No. 09/660,003, filed on Sep. 12, 2000, now U.S. Pat. No. 6,441,553, a continuation-in-part of Ser. No. 09/241,882, filed on Feb. 1, 1999, issued as U.S. Pat. No. 6,118,218.


BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to barrier films; in particular, the invention relates to films and coatings with improved barrier characteristics produced by combining precursor deposition and atmospheric glow-discharge plasma treatment with various curing steps and pre- and/or post-deposition treatments tailored to optimize end results specific to each particular applications.
2. Description of the Related Art
As detailed in U.S. Ser. No. 10/228,358, glow-discharge plasma treatment has been an effective method of treating surfaces to increase their wettability and adhesion to various materials. Glow discharge provides a uniform and homogenous plasma that produces a consistent surface treatment with high-energy electrons that collide with, dissociate and ionize low-temperature neutrals, thereby creating highly reactive free radicals and ions. These reactive species enable many chemical processes to occur with otherwise unreactive low-temperature feed stock and substrates. Based on these properties, low-density glow-discharge plasmas are usually utilized for low material-throughput processes involving surface modification.
These plasmas are typically formed by partially ionizing a gas at a pressure well below atmosphere. For the most part, these plasmas are weakly ionized, with an ionization fraction of 10−5 to 10−1, established with AC or DC power in systems with varied geometries. These systems require vacuum chambers and pumps to maintain a very low pressure, which increases operating and maintenance costs. Accordingly, there has been an extensive effort in recent years to develop plasma systems capable of operating at atmospheric pressure for surface treatment of polymer films, foils, and paper.
It is known that atmospheric plasma can be generated at relatively low temperatures with a proper power source, the insertion of a dielectric layer between the electrodes, and the use of an appropriate gas mixture as the plasma medium. For surface treatment of polymer films, fabrics, paper, etc., atmospheric plasma can be established between two electrodes using an inert gas such as helium under particular operating conditions. Usually one electrode is attached to a high voltage power supply and a rotating drum is grounded and acts as the other electrode. One electrode is coated with a ceramic layer and the plasma gas is injected between electrodes. Examples of such glow-discharge plasma systems operating at atmospheric pressure are described in U.S. Pat. Nos. 5,387,842, 5,403,453, 5,414,324, 5,456,972, 5,558,843, 5,669,583, 5,714,308, 5,767,469, and 5,789,145.
U.S. Pat. No. 6,118,218, incorporated herein by reference, disclosed a plasma treatment system capable of producing a steady glow discharge at atmospheric pressure with a variety of gas mixtures operating at frequencies as low as 60 Hz. The invention consists of incorporating a porous metallic layer in one of the electrodes of a conventional plasma treatment system. A plasma gas is injected into the electrode at substantially atmospheric pressure and allowed to diffuse through the porous layer, thereby forming a uniform glow-discharge plasma. As in prior-art devices, the material to be treated is exposed to the plasma created between this electrode and a second electrode covered by a dielectric layer. Because of the micron size of the pores of the porous metal, each pore also produces a hollow cathode effect that facilitates the ionization of the plasma gas. As a result, a steady-state glow-discharge plasma is produced at atmospheric pressure and at power frequencies as low as 60 Hz. In order for the electrode holes to operate effectively for producing an optimal glow discharge, their size must approach the mean free path of the plasma-gas at the system's operating pressure.
U.S. Pat. No. 6,441,553, herein incorporated by reference, discloses a further improvement in the art as a result of the discovery that the porous metallic layer of U.S. Pat. No. 6,118,218 may be used in conjunction with novel electrode arrangements to overcome the substrate-thickness limitations imposed by conventional plasma-treatment apparatus. In an exemplary embodiment, the invention consists of two metallic electrodes embedded side by side in a dielectric medium having an outer layer defining an exposed treatment space. One of the electrodes is made of a porous metal and serves as a conduit for introducing the plasma gas into the treatment space at substantially atmospheric pressure. The two electrodes are energized in conventional manner, using one of the electrodes as a ground, to create an electric field between them and produce a uniform glow-discharge plasma in the treatment space. Thus, the material to be treated can be exposed to the plasma so created without substantial limitation as to thickness, geometry and composition. By eliminating the need to maintain an electric field across the substrate being treated, the electrode assembly of the invention makes it possible to treat thick substrates and substrates of metallic composition that could not be treated with prior-art equipment. In addition, a powdery substrate can be treated by adding a shaker to a belt used to convey the substrate through the plasma field.
According to another advance in the use of atmospheric plasma disclosed in U.S. Pat. No. 6,441,553, herein incorporated by reference, vapor deposition is carried out in combination with plasma treatment by vaporizing a substance of interest, mixing it with the plasma gas, and diffusing the mixture through the porous electrode. A heater is provided to maintain, if necessary, the temperature of the electrode above the condensation temperature of the substance in order to prevent deposition during diffusion. Thus, plasma treatment and vapor deposition are carried out on a target substrate at the same time at atmospheric pressure.
The invention of U.S. Pat. No. 6,441,553 lies in the combination of vapor deposition and plasma treatment at atmospheric pressure using certain classes of evaporable liquid and solid materials to produce films and coatings with specifically improved barrier properties. Inasmuch as similar coatings have been produced using vapor deposition and plasma treatment under vacuum, many useful gases (i.e., vapors at ambient conditions) and vaporizable constituents are known from the prior art that can also be used advantageously in the atmospheric-pressure process of the invention (such materials are typically referred to as “precursors” in the art).
Copending U.S. Ser. No. 10/228,358, herein also incorporated by reference, provides a further development in the art of using atmospheric-plasma treatment to improve conventional deposition and surface treatment processes. A plasma gas at atmospheric pressure is used with various vapor precursors, such as silicon-based materials, fluorine-based materials, chlorine-based materials, and organo-metallic complex materials, to enable the manufacture of coated substrates with improved properties with regard to moisture-barrier, oxygen-barrier, hardness, scratch- and abrasion-resistance, chemical-resistance, low-friction, hydrophobic and/or oleophobic, hydrophilic, biocide and/or antibacterial, and electrostatic-dissipative/conductive characteristics.
The present invention is the result of further developments in the art. It discloses various atmospheric techniques wherein plasma treatment is combined with precursor deposition and other process steps common in the art, such as curing with ultraviolet, visible, or infrared light, electron-beam radiation, and pre- and/or post-deposition plasma treatment of the product.
BRIEF SUMMARY OF THE INVENTION
The gist of this invention is in the combination of the atmospheric plasma process originally rendered possible by the invention disclosed in U.S. Pat. No. 6,118,218 with various other steps known in the art of vacuum deposition in order to further improve the quality of the products obtained through atmospheric plasma processes. In particular, the invention is directed at the atmospheric-pressure manufacture of films and sheets (coating layers, in general) with improved barrier properties to moisture and oxygen for use in packaging, displays and electronic applications wherein the process of manufacture includes curing of the deposited precursor layers by exposure to UV light, or visible light, infrared light, electron-beam radiation, and the additional steps of plasma pre-and/or post-treatment.
Therefore, the invention consists of producing a plasma in a treatment space by passing a plasma gas through a porous layer and subjecting it to an electric field produced by two metallic electrodes separated by a dielectric material, and by coating a substrate material by vapor deposition or atomized spraying at atmospheric pressure in the plasma field. According to one aspect of the invention, the deposited precursor is cured by exposure to ultraviolet light in the presence of a photoinitiator, followed by further plasma treatment to enhance curing and to smooth the coated surface. The substrate may also be pre-treated in a separate plasma field to improve adhesion of the precursor layer.
In another embodiment of the invention, the substrate is first pre-treated with a plasma gas to clean the surface, a precursor is deposited in a plasma field at atmospheric pressure, and the deposited layer is cured by exposure to visible light in the presence of a photoinitiator. The coating is then post-treated with a plasma gas to enhance curing and smoothness. In another embodiment, the precursor film formed by vapor deposition is cured with an electron beam and is further post-treated with a plasma gas to enhance its finished properties. In yet another embodiment, the curing stage is accomplished with an infrared light, followed by further plasma treatment to enhance curing and to smooth the coated surface.
According to another aspect of the invention, the precursor is atomized and sprayed, rather than vapor deposited, over the substrate in the presence of a plasma field. Various precursors so deposited are then alternatively cured using UV light, IR light, visible light, or an electron-beam gun, depending on the desired finished properties, as in the case of vapor deposited precursors.
Various other purposes and advantages of the invention will become clear from its description in the specification that follows and from the novel features particularly pointed out in the appended claims. Therefore, to the accomplishment of the objectives described above, this invention consists of the features hereinafter illustrated in the drawings, fully described in the detailed description of the preferred embodiment and particularly pointed out in the claims. However, such drawings and description disclose only some of the various ways in which the invention may be practiced.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of a conventional plasma-treater configuration.
FIG. 2 is a partially cut-out, side sectional view of an electrode containing a porous-metal component according to the invention.
FIG. 3 is a schematic representation of an electrode assembly according to the invention wherein a porous-metal structure is used as an electrode as well as a perfusion medium in side-by-side combination with a conventional electrode encased in a dielectric medium.
FIG. 4 is a schematic view of an evaporator used to practice the combined vapor-deposition and plasma-treatment processes of the invention at atmospheric pressure.
FIG. 5 is a schematic view of the plasma treater configuration of FIG. 1 incorporating the evaporator of FIG. 4 for atmospheric treatment according to the invention by mixing plasma gas and coating precursor prior to injection through the electrode.
FIG. 6 is a schematic view of the plasma treater configuration of FIG. 5, wherein the coating precursor is injected directly over substrate prior to plasma treatment.
FIG. 7 is a schematic representation of an atmospheric vapor deposition system according to the invention, wherein the steps of plasma pre-treatment, vapor deposition, monomer curing, and plasma post-treatment are carried out successively in line over a moving substrate.
FIG. 8 is a schematic representation of an atmospheric deposition system as illustrated in FIG. 7, wherein the liquid precursor is atomized and deposited by spraying it over the moving substrate.
FIG. 9 is a schematic illustration of a water-cooled electrode used to diffuse plasma gas according to the invention.



DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION
This invention utilizes the advantages produced by the plasma-treatment electrodes disclosed in U.S. Ser. No. 09/660,003 and U.S. Pat. No. 6,118,218 to improve the surface properties of coated substrates manufactured by plasma-enhanced vapor deposition at atmospheric pressure. Accordingly, the invention may be carried out using the various embodiments of the apparatus described in those disclosures, which are herein incorporated by reference in their entirety. In addition, the present invention utilizes various curing and plasma-treatment units operated in line with those described in the referenced patents.
Referring to the drawings, wherein like parts are designated throughout with like numerals and symbols, FIG. 1 shows a general layout of an atmospheric plasma treater assembly wherein a plasma treater 10 is shown mounted opposite to the roller 12 of a conventional web-treatment system. A web or film 14 of material to be treated is passed through the assembly between the plasma treater and the roller at speeds typically ranging from 1 to 200 meter/min. The roller 12 is grounded and coated with a dielectric material 16, such as polyethylene teraphthalate (PET). The plasma treater 10 contains at least one electrode as described in U.S. Pat. No. 6,118,218, which is connected, through a cable 18, to an AC power supply 20 operating at any frequency between 60 Hz and the maximum frequency available from the power supply. The treater 10 is held in place conventionally by a holding bracket 22 to maintain a distance of 1–2 mm between the dielectric layer 16 and the treater 10. Plasma gas, such as helium, argon, and mixtures of an inert gas with nitrogen, oxygen, air, carbon dioxide, methane, acetylene, propane, ammonia, or mixtures thereof, can be used with this treater to sustain a uniform and steady plasma at atmospheric pressure. The gas is supplied to the treater 10 through a manifold 24 that feeds the porous electrode of the invention.
As shown in FIG. 2, an embodiment of a porous electrode 30 incorporated within the treater 10 consists of a hollow housing 32 with a porous metal layer 34 having pores sized to approximate the mean free path of the plasma gas intended to be used in the treater. The gas is fed to the upper portion 36 of the hollow electrode 30 at substantially atmospheric pressure through an inlet pipe 38 connected to the exterior manifold 24. Similarly, the electrode is energized by an electrical wire 40 connected to the power system through the exterior cable 18. The electrode 30 preferably includes a distribution baffle 42 containing multiple, uniformly spaced apertures 44 designed to distribute the gas uniformly throughout the length of the bottom portion 46 of the hollow electrode 30.
In the alternative, any one of several side-by-side embodiments of a porous electrode can be used to practice the invention, as disclosed in U.S. Pat. No. 6,441,553 and exemplified herein in FIG. 3. Such an electrode unit 50 may consist, for example, of a pair of electrodes encased in a dielectric housing 52, such as a ceramic structure. A first, conventional electrode 54 is coupled to a porous electrode 56 made of the same type of porous material described in. U.S. Pat. No. 6,118,218. The two electrodes are placed side by side facing the process space 58 where a target substrate is intended to be treated. The electrode assembly 50 is energized by an AC power source 20 and grounded through a ground 60 in conventional manner using either electrode as the ground. An inlet port 62 is connected to the porous electrode 56 to feed the plasma gas to the unit 50 through the porous metal constituting the electrode. The dielectric housing 52 between the porous electrode 56 and the boundary of the process space 58 may also include a dielectric layer 64 that consists of a porous portion capable of diffusing plasma gas received from the porous electrode into the process space. Alternatively, the porous dielectric layer 64 may be used with a hollow electrode 56 (instead of a porous electrode 56) for diffusing the plasma gas into the process space 58.
As a result of this configuration, an electric field is produced across the process space 58 when the electrode pair 54,56 is energized in conventional manner. The plasma gas is diffused at substantially atmospheric pressure through the porous electrode 56 and the dielectric layer 64 into the process space 58 where the electric field produces a steady-state glow-discharge plasma at power frequencies as low as 60 Hz. For best results, the sides 66 and 68 of the two electrodes facing the process space are substantially aligned with the exposed surface 70 of the porous dielectric layer 64, thereby promoting coupling of the two electrodes and producing an electric field across the process space along a plane aligned with the sides 66,68. Using this side-by-side embodiment of the invention, the treatment space 58 can be expanded without limitations imposed by the need to establish an electric field between the electrode and a grounded roller 12, as was the case prior to the invention disclosed in Ser. No. 09/660,003.
In order to practice the present invention, the treater assembly of FIG. 1 is preferably coupled to an evaporator 80, such as illustrated separately in FIG. 4, in order to provide the capability of evaporating liquid and solid precursors. The coating precursor to be deposited by vapor deposition on a given substrate is fed to the evaporator 80 through an inlet port 82 and is heated to its evaporation temperature by heating bands 84 at the bottom of the evaporator. If a gaseous precursor is being used, it passes through the unit without effect (or it may be passed through a bypass channel and injected directly into the plasma area). If a solid precursor is being used, it is liquefied prior to feeding it to the evaporator 80. Plasma gas is also supplied to the evaporator through a separate port 86 and is mixed with the gas or vaporized material prior to being fed to the electrode (30, 50 or equivalent porous electrode) through an outlet duct 88. FIG. 5 shows the combination of the evaporator 80 with a plasma-treatment unit of the type illustrated in FIG. 1, wherein the flow rate of, the precursor/plasma-gas mixture to the electrode is controlled by a flowmeter 90 and the flow rates of the precursor and plasma gas into the evaporator 80 are regulated by additional appropriate flowmeters 92 and 94, respectively.
As illustrated schematically with reference to the embodiment 50 of FIG. 3, a heater element 96 may also be used around the porous electrode to maintain the vaporized state of any liquid or solid precursor used in the process while the gas/vapor mixture is diffused through the porous electrode 56 (or equivalent electrode). As would be clear to one skilled in the art, the heater 96 must be capable of maintaining the electrode temperature uniformly above the vaporization temperature of the deposition material at atmospheric pressure. A temperature range from 70° C. to 100° C. has been found to be sufficient for most materials of interest. It is noted that the use of a side-by-side electrode enables plasma treatment without a dielectric coating 16 over the drum 12.
In an alternative embodiment of the invention, the evaporator 80 is used only to evaporate the precursor material, if necessary, separately from the plasma gas. The evaporated material is then injected directly in the vicinity of the plasma field, as illustrated in FIG. 6, prior to passing the substrate through the process space between the plasma treater 10 and the drum 12. The precursor vapor is injected through a slitted nozzle 98 placed across the drum 12, such that the vapor is directed for deposition toward the substrate 14 under the influence of the plasma field created by the treater 10. The plasma gas is injected separately through the porous electrode in the treater 10 to provide the plasma field in the process space.
According to still another embodiment if the invention suitable for the deposition of liquid precursors, the precursor is atomized and sprayed onto the substrate as it passes through the plasma field. Surprisingly, so long as the particle size of the atomized liquid permits the formation of a liquid film of desired thickness over the substrate, the effect of the plasma field and the subsequent curing by the same methods utilized with vapor deposition produce comparable results.
The present invention contemplates additional steps to improve adhesion and smoothness in the finished product. Accordingly, several treatment units are combined in line in a single system 100, as illustrated schematically in FIG. 7, to afford the versatility required to tailor each deposition process to the requirements of the finished product. The system 100, comprises a first conventional plasma-treatment unit 102 used to clean the surface of the web or other substrate 14 being coated while it passes continuously over the drum 12 from a feed roller 104 to a take-up roller 106. The plasma pre-treatment is used conventionally to clean the surface of the substrate to improve adhesion by removing moisture and other small molecules. A combined vapor-deposition/plasma unit 108 is then used, in the configuration detailed in either FIG. 5 or FIG. 6, to deposit a vaporized precursor as detailed in U.S. Ser. No. 10/228,358. A precursor source 110 may be incorporated into or used in conjunction with the plasma unit 108. In addition, a curing station 112 is used after the vapor deposition to polymerize the precursor and form a solid film over the substrate 14. The station 112 may consist of an infrared lamp, an electron-beam unit, an ultraviolet lamp, or a visible light source. In the last two cases, an appropriate photoinitiator is added to the precursor prior to vaporization. Finally, another plasma-treatment unit 114 is used to enhance curing and to smooth the surface of the coating film. In another embodiment of the invention illustrated in FIG. 8, the precursor is atomized, rather than vaporized, and sprayed onto the plasma-treated surface through a nozzle 120.
Organic substrates such as polypropylene, polyethylene, and polyethylene teraphthalate of various thickness were coated according to the invention using various materials with desirable properties for specific objectives. For instance, polyester substrates were coated by vapor deposition in a helium plasma at atmospheric pressure using vaporized silicon-based materials (e.g., siloxanes, alkyl silanes, silazanes, and silsesquioxanes) mixed with the plasma-gas stream and diffused into the treatment area. The resulting products exhibited improved surface properties with regard to moisture- and oxygen-barrier characteristics, hardness, scratch and abrasion resistance, chemical resistance, and low friction. The same plasma gases and fluoro-silicones were also used for vapor deposition under the same conditions by separate injection (through a slitted nozzle) and deposition over the substrate, followed by plasma treatment by passing the substrate through the treater where the plasma gas was diffused separately into the process space. Similarly positive results were obtained with fluorine-based precursors (e.g., fluorocarbons, fluoro-silicones) to provide hydrophobic and/or oleophobic properties. Chlorine-based precursors (e.g., chloro-carbons, chloro-silicones) were used to produce biocide (including antibacterial) and barrier properties; and organo-metallic complex precursors (e.g., silver, copper, boron or aluminum complex) were used to produce electrostatic, dissipative, conductive, biocidal and barrier properties.
Thus, according to the invention, the substrate is preferably pre-treated with a plasma gas in order to clean its surface, it is coated with a precursor, the deposited layer is cured according to a most appropriate method for the particular application, and an additional plasma treatment is utilized to complete curing and further improve the properties of the finished product. The following examples illustrate the combination of process steps that characterize the invention. All tests reported below are representative of many more similar tests carried out with the same materials using a helium plasma gas and a precursor in proportions varying from 10 to 98% y volume of plasma gas (about 90% plasma gas being preferred, the balance being vapor precursor). The plasma gas and the vapor precursor were fed to the treater (together or separately, as described above with reference to FIGS. 5 and 6) at a combined rate varying from about 100 to about 10,000 sccm (standard cubic centimeters per minute). In the case of atomized precursor, it was fed into the plasma gas at a rate of about 100 ml/sec (atomized) in about 500 to about 1000 sccm of plasma gas. The electrode assembly operated with a porous component with average pore size in the range of 1–20 microns. The substrate material to be treated was passed through the treatment space of 12-inch plasma treaters facing a conventional rotating drum. The tests were conducted at frequencies ranging from about 20 KHz to about 13.5 MHz.
EXAMPLE 1
Plasma Pre-Treatment; UV-Light Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 200 ft/min
    Pre-treatment:
    Plasma gas: helium fed at 2000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid fluoroacrylate monomer (with 5% Irgacure-184 photoinitiator)
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 2000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Low Pressure Mercury UV Lamp at 300 Watt/inch
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 100 sccm
    AC-voltage frequency: 15 KHz.


The resulting coated product exhibited hydrophobic and oleophobic properties with excellent adhesion to the substrate. Similar results were obtained when polypropylene, polyethylene, polycarbonate, polyamide, polyimide and cellulose derivative films were treated/coated according to Example 1. The same experiment was repeated with paper and fabrics (woven and nonwoven). Similar hydrophobicity and oleophobicity were obtained. Other precursors, such as perfluoropolyethylene glycols and fluorinated alcohols, were tested and-showed the same results.
EXAMPLE 2
Plasma Pre-Treatment; UV-Light Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 200 ft/min
    Pre-treatment:
    Plasma gas: helium with 10% oxygen fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid fluoroacrylate monomer (with 5% Irgacure-184 photoinitiator)
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 100 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Low Pressure Mercury UV Lamp at 300 Watt/inch
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 100 sccm
    AC-voltage frequency: 15 KHz


The resulting coated product exhibited hydrophobic and oleophobic properties with excellent adhesion to the substrate.
EXAMPLE 3
Plasma Pre-Treatment; UV-Light Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 200 ft/min
    Pre-treatment:
    Plasma gas: helium fed at 2000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid polyethyleneglycol monoacrylate (with 5% Irgacure-184 photoinitiator)
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 2000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Low Pressure Mercury UV Lamp at 300 Watt/inch
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 15 KHz


The resulting coated product exhibited hydrophilic and anti-fog properties with excellent adhesion to the substrate. Similar results were obtained when polypropylene, polyethylene, polycarbonate, polyamide, polyimide and cellulose derivative films were treated/coated according to Example 3. The same experiment was repeated with paper and fabrics (woven and nonwoven) and similar hydrophilicity and anti-fog properties were obtained.
EXAMPLE 4
Plasma Pre-Treatment; UV-Light Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 200 ft/min
    Pre-treatment:
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid acrolin and/or chlorinated acrylate with 5% Irgacure-184 photoinitiator)
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Low Pressure Mercury UV Lamp at 300 Watt/inch
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 15 KHz


The resulting coated product exhibited biocide, anti-bacterial properties with excellent adhesion to the substrate. Similar results were obtained when polypropylene, polyethylene, polycarbonate, polyamide, polyimide and cellulose derivative films were treated/coated according to Example 4. The same experiment was repeated with paper and fabrics (woven and nonwoven) and similar biocide properties were obtained.
EXAMPLE 5
Plasma Pre-Treatment; Visible-Light Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 200 ft/min.
    Pre-treatment:
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid fluoroacrylate monomer (with 5% H-NU-635 photoinitiator)
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Tungsten-Halogen Lamp at 100 Watt/inch
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 20 KHz


The resulting coated product exhibited hydrophobic and oleophobic properties with excellent adhesion to the substrate.
EXAMPLE 6
Plasma Pre-Treatment; Visible-Light Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 200 ft/min
    Pre-treatment:
    Plasma gas: helium with 10% oxygen fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid fluoroacrylate monomer (with 5% H-NU-635 photoinitiator)
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Tungsten-Halogen Lamp at 100 Watt/inch
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 15 KHz


The resulting coated product exhibited hydrophobic and oleophobic properties with excellent adhesion to the substrate.
EXAMPLE 7
Plasma Pre-Treatment; Visible-Light Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 200 ft/min
    Pre-treatment:
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid polyethyleneglycol monoacrylate (with 5% H-NU-635 photoinitiator)
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Tungsten-Halogen Lamp at 100 Watt/inch
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 15 KHz


The resulting coated product exhibited hydrophilic and anti-fog properties with excellent adhesion to the substrate.
EXAMPLE 8
Plasma Pre-Treatment; Visible-Light Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 200 ft/min
    Pre-treatment:
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid acrolin and/or chlorinated acrylate with 5% H-NU-635 photoinitiator)
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Tungsten-Halogen Lamp at 100 Watt/inch
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 15 KHz


The resulting coated product exhibited biocide, anti-bacterial properties with excellent adhesion to the substrate.
EXAMPLE 9
Plasma Pre-Treatment; IR-Light Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 20 ft/min
    Pre-treatment:
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid fluoroacrylate monomer
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Infrared Lamp at 500 Watt
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 15 KHz


The resulting coated product exhibited hydrophobic and oleophobic properties with excellent adhesion to the substrate.
EXAMPLE 10
Plasma Pre-Treatment; IR-Light Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 20 ft/min
    Pre-treatment:
    Plasma gas: helium with 10% oxygen fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid fluoroacrylate monomer
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Infrared Lamp at 500 Watt
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 15 KHz


The resulting coated product exhibited hydrophobic and oleophobic properties with excellent adhesion to the substrate.
EXAMPLE 11
Plasma Pre-Treatment; IR-Light Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 20 ft/min
    Pre-treatment:
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid polyethyleneglycol monoacrylate
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Infrared Lamp at 500 Watt
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 15 KHz


The resulting coated product exhibited hydrophilic and anti-fog properties with excellent adhesion to the substrate.
EXAMPLE 12
Plasma Pre-Treatment; IR-Light Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 20 ft/min
    Pre-treatment:
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid acrolin and/or chlorinated acrylate
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Infrared Lamp at 500 Watt
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 15 KHz


The resulting coated product exhibited biocide, anti-bacterial properties with excellent adhesion to the substrate.
EXAMPLE 13
Plasma Pre-Treatment; Electron-Beam Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 200 ft/min
    Pre-treatment:
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid fluoroacrylate monomer
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Electrocurtain (Energy Science, Inc.)
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 15 KHz


The resulting coated product exhibited hydrophobic and oleophobic properties with excellent adhesion to the substrate.
EXAMPLE 14
Plasma Pre-Treatment; Electron-Beam Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 200 ft/min
    Pre-treatment:
    Plasma gas: helium with 10% oxygen fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid fluoroacrylate monomer
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Electrocurtain (Energy Science, Inc.)
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 15 KHz


The resulting coated product exhibited hydrophobic and oleophobic properties with excellent adhesion to the substrate.
EXAMPLE 15
Plasma Pre-Treatment; Electron-Beam Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum-Speed: 200 ft/min
    Pre-treatment:
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid polyethyleneglycol monoacrylate
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Curing:
    Electrocurtain (Energy Science, Inc.)
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 15 KHz Curing:


The resulting coated product exhibited hydrophilic and anti-fog properties with excellent adhesion to the substrate.
EXAMPLE 16
Plasma Pre-Treatment; Electron-Beam Curing; Plasma Post-Treatment


    Substrate material: PET film
    Drum Speed: 200 ft/min
    Pre-treatment:
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 KHz
    Deposition:
    Precursor: liquid acrolin and/or chlorinated acrylate
    Evaporator temperature: 200–250° C.
    Mixing step: mixed with plasma gas prior to injection
    Feed rate of vaporized precursor: 200 sccm
    Plasma gas: helium fed at 3000 sccm
    AC-voltage frequency: 20 kHz
    Curing:
    Electrocurtain (Energy Science, Inc.)
    Post-Treatment:
    Plasma gas: helium with 5% acetylene fed at 3000 sccm
    AC-voltage frequency: 15 KHz


The resulting coated product exhibited biocide, anti-bacterial properties with excellent adhesion to the substrate.
Similar results were obtained by injecting the vaporized precursor directly into the plasma filed, rather than mixing it with the plasma gas prior to injection. A similar set of tests was also performed using a liquid atomizer, as illustrated schematically in FIG. 8, rather than an atmospheric vapor deposition system. The results were surprisingly similar to the ones achieved in Examples 1–16. The photoinitiators were mixed and atomized with the liquid precursors and, after deposition, they were cured using the same various treatment steps illustrated above.
In some instances, a water cooled electrode, as illustrated in FIG. 9, was used in the production of the plasma field. This enabled the application of greater power to the system. In operation, such an electrode 130 is oriented so that its curved surface 132 faces the process space and the grounded process drum. A plasma gas blanket is established in the plasma region below the curved surface 132 by feeding plasma gas into porous diffusion channels 134. Cooling is established by pumping coolant through cooling channels 136. Dielectric barrier plates 140 are affixed to the outer surface of the electrode to provide containment of the plasma gas at the exterior surface of the electrode assembly. The electrode is electrified with a high voltage source and a partial discharge is generated immediately below the dielectric surface 138. A substrate to be treated is transported in conventional manner through the plasma region on the outer surface of the grounded process drum.
These data show that the invention advantageously enables the production of plasma-enhanced coated substrates at atmospheric-pressure conditions with properties equal to or better than previously obtained under vacuum plasma conditions. These results show that the electrodes of the invention can be used for treating and modifying the surface properties of organic as well as inorganic substrates without vacuum equipment or material-thickness limitations. In addition, they demonstrate that deposited precursors may be cured by alternative means with the appropriate addition of photoinitiators, as well understood in the art, in order to tailor the treatment and the application to specific desired results.
Based on their known properties, it is anticipated that a large variety of other polymerizable compounds can be used as precursors with this invention. They include the following:
1. Unsaturated alcohols and esters thereof: allyl, methallyl, 1-choroallyl, 2-chloroallyl, vinyl, methylvinyl, 1-phenalallyl, and butenyl alcohols; and esters of such alcohols with saturated acids such as acetic, propionic, and butyric; with unsaturated acids such as acrylic, α-substituted acrylic (including alkylacrylic, such as methacrylic, ethylacrylic, propylacrylic, etc.; and arylacrylic, such as phenylacrylic), crotonic, oleic, linoeic and linolenic, and with polybasic acids, such as oxalic, and malonic.
2. Unsaturated acids (as listed above for example); and esters thereof with lower saturated alcohols, such as methyl, ethyl propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, and cyclohexyl alcohols; and with saturated lower polyhydric alcohols, such as ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, and trimethylopropane.
3. Unsaturated lower polyhydric alcohols, such as butenediol; and esters thereof with saturated and unsaturated aliphatic and aromatic, monobasic and polybasic acids, such as illustrated above.
4. Esters of the above-described unsaturated acids, especially acrylic and methacrylic acids, with higher molecular-weight monohydroxy and polyhydroxy materials, such as decyl alcohol, isodecyl alcohol, oleyl alcohol, and stearyl alcohol.
5. Vinyl cyclic compounds including styrene, o-, m-, p-chlorostyrenes, bromostyrenes, fluorostyrens, methylstyrenes, ethylstyrenes, cyanostyrenes; di-, tri-, and tetrachlorostyrenes, bromostyrenes, fluorostyrenes, methylstyrenes, ethylstyrenes, cyanostyrenes, vinylnaphthalene, vinylcyclohexane, divinylbenzene, trivinylbenzene; allybenzene, and heterocycles-such as vinylfuran, vinnylpridine, vinylbenzofuran, N-vinylcarbazole, N-vinylpyrrolidone, and N-vinyloxazolidone.
6. Unsaturated ethers, such as methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, octyl vinyl ether, diallyl ether, ethyl methallyl ether, and allyl ethyl ether.
7. Unsaturated ketones, such as methyl vinyl ketone and ethyl vinyl ketone.
8. Unsaturated amides, such as acrylamide, methacrylamide, N-methylacrylamide, N-phenylolacrylamide, N-allylacrylamide, N-methylolacrylamide, N-allylcaprolactam, diacetone acrylamide, and 2-acrylamido-2-methylpropanesulfonic acid.
9. Unsaturated aliphatic hydrocarbons, such as ethylene, acetylene, propylene, butanes, butadiene, isoprene, and 2-chlorobutadiene.
10. Unsaturated alky halides, such as vinyl fluoride, vinyl chloride, vinyl bromide, nylidene bromide, allyl chloride, and ally bromide.
11. Unsaturated acid anhydrides, such as maleic, citraconic, itaconic, cis-4-cyclohexene-1,2-dicarboxylic, and bicyclo(2.2.1)-5-heptene-2,3-dicarboxylic anhydrides.
12. Unsaturated acid halides, such as cinnamyl acrykyl, methacrylyl, crontonyl, oleyl, and fumaryl chlorides or bromides.
13. Unsaturated nitrites, such as acrylonitriles, methacrylonitrile, and other substituted acrylonitriles.
Various changes in the details, steps and components that have been described may be made by those skilled in the art within the principles and scope of the invention herein illustrated and defined in the appended claims. Therefore, while the present invention has been shown and described herein in what is believed to be the most practical and preferred embodiments, it is recognized that departures can be made therefrom within the scope of the invention, which is not to be limited to the details disclosed herein but is to be accorded the full scope of the claims so as to embrace any and all equivalent processes and products.

## Claims

1. A method for manufacturing a coated substrate by a process of vapor deposition and concurrent glow-discharge plasma treatment at substantially atmospheric pressure, comprising the following steps:
providing a first electrode and a second electrode separated by a dielectric material and facing a process space:
applying a voltage across the electrodes;
mixing a vaporized precursor with a plasma gas;
diffusing the vaporized precursor and plasma gas through a porous material into the process space at substantially atmospheric pressure;
depositing the vaporized precursor over said substrate; and
curing the precursor to produce a polymeric film.

2. The method of claim 1, wherein said curing step is carried out with ultraviolet radiation.

3. The method of claim 1, wherein said curing step is carried out with visible light.

4. The method of claim 1, wherein said curing step is carried out with infrared radiation.

5. The method of claim 1, wherein said curing step is carried out wit electron-beam radiation.

6. The method of claim 1, further including the step of pre-treating the substrate in a plasma field prior to the step of depositing the vaporized precursor.

7. The method of claim 1, further including the step of post-treating the polymeric film in a plasma field after the step of curing the vaporized precursor.

8. The method of claim 6, further including the step of post-treating the polymeric film in a plasma field after the step of curing the vaporized precursor.

9. The method of claim 8, wherein said curing step is carried out with ultraviolet radiation.

10. The method of claim 8, wherein said curing step is carried out with visible light.

11. The method of claim 8, wherein said curing step is carried out with infrared radiation.

12. The method of claim 8, wherein said curing step is carried out electron-beam radiation.

13. A method for manufacturing a coated substrate by a process of vapor deposition and concurrent glow-discharge plasma treatment at substantially atmospheric pressure, comprising the following steps:
providing a first electrode and a second electrode separated by a dielectric material and facing a process space;
applying a voltage across the electrodes;
diffusing a plasma gas through a porous material into the process space at substantially atmospheric pressure;
depositing a vaporized precursor over said substrate upstream of the process space; and
curing the precursor to produce a polymeric film.

14. The method of claim 13, wherein said curing step is carried out with ultraviolet radiation.

15. The method of claim 13, wherein said curing step is carried out with visible light.

16. The method of claim 13, wherein said curing step is carried out with infrared radiation.

17. The method of claim 13, wherein said curing step is carried out electron-beam radiation.

18. The method of claim 13, further including the step of pre-treating the substrate in a plasma field prior to the step of depositing the vaporized precursor.

19. The method of claim 13, further including the stop of post-treating the polymeric film in a plasma field after the step of curing the vaporized precursor.

20. The method of claim 18, further including the step of post-treating the polymeric film in a plasma field after the step of curing the vaporized precursor.

21. The method of claim 20, wherein said curing step is carried out with ultraviolet radiation.

22. The method of claim 20, wherein said curing step is carried out with visible light.

23. The method of claim 20, wherein said curing step is carried out with infrared radiation.

24. The method of claim 8, wherein said curing step is carried out electron-beam radiation.

25. The method of claim 13, wherein said depositing step is carried out by atomizing and spraying said precursor over the substrate in line with the plasma gas.

26. The method of claim 18, wherein said depositing step is carried by atomizing and spraying said precursor over the substrate in line with the plasma gas.

27. The method of claim 19, wherein said depositing step is carried out by atomizing and spraying said precursor over the substrate in line with the plasma gas.

28. The method of claim 20, wherein said depositing step is carried by atomizing and spraying said precursor over the substrate in line with the plasma gas.