JP2002532828A - Array of hollow cathodes for plasma generation - Google Patents

Abstract

SUMMARY The present invention relates to a cathode assembly for use in generating a discharge plasma. The cathode comprises a plurality of electrically conductive hollow plasma generating cells in an array, the cells being electrically connected to one another. The generated plasma can be used to modify the properties of the surface of the substrate, such as films, fibers, particles, and other products.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION The present invention relates to an array of hollow cathodes for use in generating a discharge plasma. The generated plasma can be used to modify the surface properties of substrates such as films, fibers, particles and other products.

[0002] The treatment of various substrates, such as polymers, to provide new surface properties by physical or chemical modification is important in a number of industries, including the film industry. Wet methods have been used successfully for these treatments, but such wet methods involve problems such as solvent waste disposal. Dry methods such as corona treatment, uv treatment, laser treatment, x-ray and gamma-ray treatment have also been used with some success.
Corona treatment has been used in the industry for decades, but is generally constrained to simple surface structures, such as web structures. In addition, for some materials, the effect of corona treatment diminishes over time. Furthermore, there is little control over what functional groups can be created on the surface of the treated substrate, and the close distance between the electrode and the substrate is
This can result in the undesirable formation of pinholes or burnt areas. UV,
X-ray, gamma-ray and laser treatments are point light sources and cannot be easily used to process large areas. Furthermore, these processes are subject to the effects of intensity fluctuations or shadows, which can result in some regions receiving less processing or even occluded by shadows in the visibility range.

[0003] The treatment of hard, shaped or molded polymer containers to provide improved surface properties and gas barrier properties is important in the food and beverage industry. Various methods of application have been proposed to coat these containers with various compositions and thereby improve their gas barrier properties. However, there is a continuing need to further increase the gas shielding properties of these containers so that they can be more retarded in the permeation of gases such as oxygen and carbon dioxide. Furthermore, there is a continuing need for improved surface properties, especially in relation to printability, to improve the reusability of these containers.

[0004] Although plasma technology has been used in laboratories for over 50 years, it has only recently been implemented on a commercial scale, primarily driven by the semiconductor industry. In the plasma treatment of polymers, energetic particles and photons generated in the plasma react strongly with the surface of the polymer, usually by free radical chemistry.

[0005] A major advantage of plasma surface treatment compared to other treatment methods is that there are no harmful by-products. Normally, there are no toxic or hazardous liquids or gases that must be disposed of. Usually, by-products of the main processes for the plasma treatment is CO, CO ₂ and water vapor, not present in amounts having their none toxicity. In theory, plasmas can be applied to objects with all possible geometries, with varying success rates, by using conventional equipment and methods. These objects include large amounts of small, discrete materials, such as webs, films, large solid materials of complex morphology, and powders.

[0006] A major obstacle to using plasma processes on an industrial scale is the achievement of economically acceptable production rates. The convenience of the plasma method is readily apparent, but because of the very low throughput, the method is economically available only for products that gain significantly increased value from the method. Limiting factors include low plasma intensity and lack of plasma binding. Plasma modification or polymerization systems with the potential for high production rates will provide rapid growth in the use of plasma engineering on an industrial scale.

[0007] Most devices used to generate a plasma for plasma polymerization and plasma modification use two basic types of electrode configurations, variants of internal parallel plate electrodes and external electrodes. is there. The convenience of these two methods is due to the ease with which they can be scaled up to process large areas while maintaining high plasma intensity such that a minimum residence time can be achieved. Be constrained. Existing DC hollow cathode plasma reactors provide higher plasma intensity and a higher degree of plasma containment than internal parallel plates and external electrodes. However, large hollow cathode reaction vessels are inherently difficult to scale up, so they cannot be used to process large areas. To achieve the desired plasma intensity in the large hollow cathode reactor required to accommodate a large area process such as a 60 ″ (152.4 cm) wide substrate, very high voltages are required. is necessary.

[0008] EP 634 778 describes an array of hollow cathodes that generate a plasma for surface etching and removal of "rolling oil" on metal sheets. The hollow cathode array system comprises a housing having a plurality of openings uniformly spaced along one wall of the housing. The hollow cathode plasma is basically generated in the housing and transported through the opening. Such an array of openings acts as a distributor but does not increase plasma intensity and uniformity. Each opening has a diameter of about 1/16 inch (0.15 cm). The pressure used in the system of EP 634 778 is in the range of 0.1 to 5.0 Torr and the power applied is in the range of 0.5 to 3.0 kW.

US Pat. No. 5,686,789 describes a discharge device having a cathode with a fine hollow array for use in subminiature fluorescent lamps. This patent covers devices with dimensions of the mean free path magnitude of electrons that cannot be performed for large area processing. The electrons undergo an oscillating motion within the fine hollow, which results in a fine hollow discharge, increasing the current capability. US Patent 5,6
The 86,789 system uses a pressure of 0.1 Torr to 200 Torr in use. The patent does not mention reactive plasma, plasma polymerization, or surface modification of materials.

[0010] “Hollow cathodic discharge spatterin
g device for uniform large area thin
film deposition, "(J. Vac. Sol. Technol.
. A9 (4), Jul / Aug 1991, p. 2374) in an article entitled H
. Koch et al. Describe a hollow cathode discharge device that generates sputtered particles having a higher strength than a conventional discharge body. In the hollow cathode plasma sputtering method described therein, a sputtering target, such as Cu, is used as the cathode. The method is primarily a physical method in which the movement of momentum occurs. The article mentions the use of hollow cathode discharge devices when generating a reactive plasma for surface modification or when performing plasma polymerization to coat a thin layer on a substrate surface. I haven't.

Wherein the treatment can be adapted to (1) solvent-free and / or harmful by-products, (2) any surface structure, any size and / or chemistry of a product, (3) provides uniform processing, (4) enables high throughput at high speeds, (5) can be used in batch or continuous processes, and (6) at low pressure or under other desirable conditions There is a continuing need for methods for surface treatment that can be operated.

SUMMARY OF THE INVENTION The present invention relates to a method for forming a plurality of electrically conductive hollow plasma generating cells in an array, wherein:
The cell is electrically connected to each other) for generating a plasma.

The present invention also includes an assembly of at least one type of cathode as described above, an apparatus for supplying a gas of a plasma precursor to the assembly of cathodes, and an apparatus for supplying power to the assembly of cathodes. To a plasma generator.

The present invention further provides for positioning a substrate in close proximity to the at least one cathode assembly and providing at least one plasma precursor gas proximal to the cathode assembly and the substrate. Generating a plasma by applying power to the assembly of cathodes, and exposing the surface of the substrate to the plasma for a time sufficient to form a treated surface. A method of treating the surface of

The present invention also provides (a) forming a molded biaxially oriented polymer container, and (b) assembling the inventive cathode as described herein, wherein at least one surface of the container is in the form of an array. Exposing to a plasma generated from a gas of a plasma precursor comprising a hydrocarbon, (c) introducing a liquid into the vessel, and
d) sealing the container, comprising filling the liquid into a molded biaxially oriented polymer container.

The present invention further comprises exposing the polyester substrate to a plasma generated from a plasma precursor gas comprising a hydrocarbon using the inventive cathode assembly described herein. And a method for reducing the gas permeability of a polyester substrate.

DETAILED DESCRIPTION Referring initially to FIGS. 1-6 and 10-13, generally an alternative embodiment of the cathode assembly of the present invention is shown. Cathode assembly 1 includes a plurality of cells 2 that together form an array of individual plasma generators. Each cell is defined by one or a plurality of walls 3. The assembly of cathodes comprises a plurality of electrically conductive hollow plasma generating cells installed in an array, the cells being electrically connected to each other, the cells having a small or large processing area. It is effective to provide uniform plasma processing to a proper substrate.

By “hollow plasma generating cell” is meant a plurality of cells, each cell being defined by at least one wall. The cells defined by one or more walls may have any form. However, for ease of manufacture, the cells preferably have a generally circular cross-sectional configuration, a generally elliptical cross-sectional configuration, a generally regular or irregular polygonal cross-section. It has the form of a surface, or any combination of those forms (see FIGS. 1-6 and 10-13). "Regular polygons"
Means a cross-sectional form selected from the group consisting of triangles, parallelograms, pentagons, hexagons, heptagons, octagons, and combinations thereof. For cells having irregular polygonal cross-sectional configurations, the configurations may be the same or different.

The cell can be tube-like with two open ends. Alternatively, the cells are further defined by a base 5 on which one open end of the cell is mounted (see especially FIG. 10), or each cell is one end of the cell. Can be further defined by a distal end 6 surrounding the Accordingly, the cell may further comprise one end of the cell, wherein such an end is planar, has a flat bottom, is U-shaped, V-shaped, or otherwise (see FIGS. 7-9). It may comprise a surrounding end. The tube-like cells or the cells further defined by the ends can be placed on a planar or shaped base 5.

For ease of handling and / or connection to a power supply, the assembly of the cathode can further comprise one or more side parts 8 which can surround the array of cells. In some embodiments, the side pieces 8 may form the entire cell wall or a portion thereof. The side pieces 8 can be attached to at least part of the cells on the periphery of the array and / or can be attached to the optional base 5. Holes 4 in the side components can facilitate connection to a power supply.

Generated by a “plasma” under the influence of extreme thermal conditions or electric / magnetic fields,
A gas that is completely or partially ionized. Plasma rapidly decomposes energetic ions, photons, electrons, highly reactive chemicals, neutral stables, excited molecules, and any gases present to form atoms. A volume of high energy electric and magnetic fields.

By “array” is meant any shaped group of cells. This can include a planar array or an array with a morphology. The array can further include any random arrangement of cells, wherein the cells are arranged to effect processing only on selected areas of the substrate.

A single wall, a plurality of walls, and / or an optional end portion or case, by which the cell is defined or on which the cell can be placed by “electrical conductivity” Means that the base used comprises a material capable of conducting electricity. "Electrically connected to each other" means that when the cathode assembly is connected to a power source, the cells are in electrical contact with each other, thanks to the electrically conductive material that separates each cell. It means you can do it. Materials useful in the manufacture of the cathode assembly of the present invention include, but are not limited to, stainless steel, aluminum, titanium, copper, tungsten, platinum, chromium, nickel, zirconium, molybdenum or their alloys with each other or other known elements. And any electrically conductive material that would not adversely affect the plasma process.

Although the cell openings can have various cross-sectional dimensions, the plurality of cells in the array may range from about 0.1 to about 5.0, most preferably about 0.2.
Preferably, it has a ratio of the area of the cell cross section to the cell depth in the range of 5 to about 4.0. Preferably, the cross-sectional area of each cell ranges from about 0.25 to about 10 in ² (about 1.6 to about 64.5 cm ² ).

Each cell can be defined by one or more separated walls whose walls are not shared by adjacent cells (see FIGS. 2, 5, 6 and 10). . These cells can be separated from at least one neighboring cell (see FIG. 6) or have a wall in contact with at least one wall of at least one neighboring cell (see FIG. 6). (See FIG. 2) or any combination thereof. Alternatively, adjacent cells can share at least one common wall (see FIGS. 1, 3, 4, and 11). Preferably, adjacent cells having a regular or irregular polygonal form share at least one common wall or at least one wall of at least one adjacent cell It has a wall in contact with Each wall has a thickness that is conductive and has mechanical integrity.

All or a portion of at least one wall of at least one cell of the cathode assembly of the present invention can be coated with a dielectric material 10 (see cathode assembly on the left side of FIG. 11). Additionally or alternatively, the dielectric material 10 can be located adjacent to at least one cell of the cathode assembly of the present invention (
See the cathode assembly on the right side of FIG. 11). These dielectric materials are mica,
It can include ceramic or a polymer material with a high dielectric constant. The dielectric material may be coated around the edges of the cell, cover all or part of the surface of the cell wall, or cover the surface immediately adjacent to the cell. The dielectric material prevents arcing and short circuits and can quench the discharge. The dielectric material can be used to mask certain cells and thus prevent plasma generation from the cells when the cathode assembly is being used. Decorative effects can be implemented on the substrate by obscuring some cells during the plasma treatment of the substrate.

In order to provide a more uniform plasma treatment, it may be advantageous to provide at least a portion of the cells adjacent to the periphery of the array with a smaller cross-sectional area than the cells inside the array. It's been found. This aspect compensates for the loss of diffusion (FIGS. 2, 3).
, 4, 5 and 6).

The cells of the cathode can be arranged in a generally planar array of preferred embodiments for the treatment of planar substrates 12 (see FIG. 11). Alternatively, the cells of the assembly of the cathode may be the product to be processed, e.g., curved, ring-like or
It can be arranged in a shaped array to accommodate product forms with other forms 14 (see FIG. 10) such as bottles (see FIG. 12 or 13). A curved array having such a configuration can be concave or convex, for example. 12 and 13, the cathode assembly 1 is placed in a bottle-shaped container 20 for plasma treatment of the inner surface of the container. The outer electrode 30 is shown as having a cell-like configuration, but could have a simple flat surface. In the embodiment shown in FIGS. 12 and 13, the polarity could be reversed and a gas supply could be provided to the electrode 30 so that the outer surface of the bottle-shaped container 20 could be treated.

One or more walls of the cell are located on the entire surface of the array (see FIG. 7).
, Or substantially perpendicular to the plane of that portion of the array on which the particular cell is located. Alternatively, one or more walls of each cell may be in the plane of the array (see FIGS. 8 and 9) or in that part of the array on which the particular cell is located. It may have at least a portion of a single wall forming an obtuse angle to it.

The configuration of the array preferably matches the configuration of the substrate so as to maintain a reasonably uniform spacing between the cell assembly and the portion of the substrate to be treated. Such reasonably uniform spacing allows for more uniform processing.

The cathode assembly of the present invention can be manufactured by mechanically cutting conductive material into parts of a desired length, width and thickness, and placing these parts in a desired array of arrays. it can. The parts can be fitted together in an array of slots, placed in a tight array so as to be wedged together, or welded by a typical sheet metal spot welding process. Other methods of processing the cathode assembly of the present invention will be readily apparent to one of ordinary skill in the art.

The present invention also provides a cathode generator, a device for supplying a gas of a plasma precursor to the cathode assembly, and a plasma generator comprising a device for supplying power to the cathode assembly. See FIG. 11).

Supplying the plasma precursor gas by a gas jet 16 (see FIGS. 7, 12 and 13) positioned relative to the cathode assembly such that the precursor gas diffuses proximally of the cell. Can be. FIG. 7 shows manifolds 16M each connected to an individual gas jet 16 located in the cell. FIG.
2 and 13 also show a manifold 16M connected to individual gas jets 16 located in a central electrode located inside the bottle 20. The plasma gas can be supplied through a plasma gas supply line (not shown), and the gas mass flow is controlled by MKS Instrument, Inc. MK for sale from
It can be controlled using a suitable plasma gas flow controller such as S Type 1179A. The flow rate depends on the application method. Many applications are about 0.1 per minute
It can be suitably handled using a flow rate of from about 100 standard cubic centimeters (sccm), preferably about 0.5 to 15 sccm. Other applicable laws are:
It can be handled using higher or lower flow rates.

The power supply 18 (see FIG. 11) can use a DC source or an AC source that operates at audio frequency (AF) or radio frequency (RF). A power supply can be inserted into hole 4 in one embodiment, a suitable securing device (not shown)
Is connected to the cathode assembly. 1k for many application methods
Less than W power is required, preferably about 1 to about 1000 kW, and most preferably about 5 to about 200 watts are used. However, there are applications where more than 1 kW of power input is required to achieve the desired result. In such a case, a liquid electrode cooling system can be used.

A low pressure (in vacuum) is used for the plasma processing of the present invention. Accordingly, the plasma generator of the present invention further comprises a vacuum chamber in which the assembly of the cathode fits, and an apparatus for providing a vacuum. A suitable vacuum chamber, such as a cylindrical stainless steel vacuum chamber, has been found to be suitable. Edwards High Vacuu
Commercial vacuum pumps can be used, including booster pumps in combination with rotary pumps, such as the E2M80 / EH500 from m International. Pressures useful in the present invention can range from about 1 mTorr to about 100 Torr, preferably 1 mTorr to about 1 Torr. Batch or continuous processing is possible when using the plasma generator or method of the present invention.
While vacuum systems tend to lend themselves to batch processing, the use of a staged vacuum system allows continuous processing to be maintained at sub-atmospheric pressures.
By "staged vacuum system" is meant a series of chambers under different pressures.

[0036] The present invention further provides, in close proximity to said at least one cathode assembly,
Disposing at least one surface of the substrate, proximate the assembly of the cathode and the substrate;
Supplying a gas of at least one plasma precursor, generating a plasma by supplying power to the cathode assembly, and subjecting the plasma to the substrate for a time sufficient to form a treated surface. Exposing at least one surface to a method of treating at least one surface.

First, at least one surface of the substrate is located in close proximity to the at least one cathode assembly. By "proximal" it is meant that the substrate is at a suitable distance from the cathode assembly sufficient to undergo plasma treatment. One or more cathode assemblies can be used to treat the substrate. Substrates useful for the treatment of the present invention include fibers, films, particles, and products in the form of bottles or other containers. The substrate can be spaced parallel to and at a preselected distance from the at least one cathode assembly of the present invention. When using a morphological cathode assembly, it is preferable to maintain a reasonably uniform distance between the substrate and the cell to provide uniform processing of the substrate.

[0038] The substrate of the fiber, film, particle or morphological article can be made from a thermoplastic polymer material. Films and rigid containers contemplated for use in the present invention include those formed from conventional thermoplastic polymers such as polyolefins, polyamides, and engineering polymers such as polycarbonates. The invention is
Diethylene glycol, propane-1, wherein up to about 50 mole percent or more of the copolymer is substituted for a glycol moiety in the preparation of the copolymer.
, 3-diol, butane-1,4-diol, polytetramethylene glycol,
Polyethylene glycol, polypropylene glycol and 1,4-hydroxymethylcyclohexane, or isophthalic acid, dibenzoic acid, naphthalene 1,4- or 2,6-dicarboxylic acid substituted for an acid moiety in the preparation of a copolymer, Polyethylene terephthalate (PET), including homopolymers and copolymers of ethylene terephthalate and ethylene naphthalate, which can be prepared from monomer units of adipic acid, sebacic acid, and decane-1,10-dicarboxylic acid Film and rigid, i.e., containers and injection stretch blow molding, such as bottles, formed from synthetic linear polyesters such as polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc. Biaxial stretching hollow heat It is applicable to plastic containers. The foregoing description is intended as a specific description of the applicable polymer substrate, and is not intended to limit the scope of the invention.

Second, in the method, at least one plasma precursor gas is provided proximal to the cathode assembly and the substrate. Plasmas fall into three categories: (1) chemically non-reactive plasma, (2) chemically reactive but non-polymer forming plasma, and (3) chemically reactive, polymer forming plasma. Can be classified. The plasma precursor gas used can be selected based on the desired processing provided by the plasma. Suitable precursor gases include, for example, gases comprising hydrocarbons such as nitrogen, hydrogen, oxygen, ozone, nitrous oxide, methane, ethylene, butadiene or acetylene, argon, helium, ammonia, etc. Possible hydrogen / nitrogen mixtures, mixtures of gases such as air, halides, halocarbons, and polymerizable monomers. For example, the polymer film can be treated with virtually any organic or metal organic compound that can be introduced into the plasma discharge zone. One or more precursor gases are supplied by a gas jet at a desired gas flow rate into the vacuum chamber.

The plasma is generated by powering the cathode assembly. The cathode assembly is connected to a power supply and switches on the power supply to initiate a plasma condition. Next, the power is adjusted to the desired power level. The power level can be varied based on gas flow rate, substrate size, distance from the cathode assembly to the anode, the molecular weight of the plasma precursor gas, and the pressure. The power and gas flow rates can be adjusted to create an intense plasma discharge in all desired cells of the cathode assembly. In some cases, magnetic enhancement can be used to focus the plasma as it exits the cell.

Finally, at least one surface of the substrate is exposed to the plasma for a time sufficient to form a treated surface. Plasma treatment must be maintained for a desired period of time, which can range from seconds to minutes. The processing time depends on the characteristics of the plasma and its interaction with the substrate surface depending on the operating parameters under which the plasma is maintained.
These parameters include gas flow, input power, pressure, discharge power and substrate location. Processing time can also depend on the nature of the substrate.

The present invention is useful for filling beverages. Accordingly, the present invention further provides for forming a container, using the assembly of the inventive cathode described herein, wherein the array is in the form, generated from a gas of a plasma precursor comprising a hydrocarbon. Exposing at least one surface of the vessel to the plasma, introducing a liquid into the vessel,
And sealing the container, comprising filling the molded biaxially oriented polymer container with a liquid. The method may further comprise evacuating the gas from the container before introducing the liquid. This method may be suitable for carbonated liquids.

The present invention relates to poly (ethylene terephthalate) films and rigid containers used for packaging food and beverages and injection stretch blow molded PET bottles used for filling carbonated soft drinks and beer. , Suitable for improving gas shielding properties. Accordingly, the present invention provides for the use of the cathode assembly of the present invention described herein to subject at least one surface of a polyester substrate to a plasma generated from a plasma precursor gas comprising a hydrocarbon. A method for reducing the gas permeability of a polyester substrate comprising exposing.

The present invention is directed to surface cleaning (removal of organic contaminants), etching or ablation (
Removal of weak boundary layers and increase of surface area), cross-linking or branching of molecules close to the surface, which can enhance the surface layer and thus the physical properties together, of surface areas with novel chemical functionality Chemical modification / grafting by planned changes, as well as changing the surface properties of the substrate to meet the needs of thin film coating, deposition, or thin, pinhole-free membranes in permeable-selective membranes It is useful in methods involving barrier coatings to take advantage of the internal properties of highly adhesive films.

[0045]

【Example】

Example 1 Increased Adhesion of Polyimide Film to Copper Two Types of 12-in.times.12 having a square cell pattern similar to that shown in FIG.
The in-cathode assembly was manufactured from stainless steel. Each cell is 1in × 1i
It has a measurement of n × 1 in and the ratio of the area of the cell cross section to the cell depth is 1.
It was equal to zero. The two cathode assemblies were placed parallel to each other in a vacuum chamber, and each cathode was connected to a DC power supply. E. FIG. I. Du Pont de N
emours and Company, Wilmington, disposed between the cathode Kapton ^(R) polyimide film available from DE at a distance of about 2in from each cathode. The vacuum was introduced at a pressure of 150 mTorr. Ammonia, 1 per minute
It was introduced into the room at a flow rate of 2 standard cubic centimeters (sccm) and was powered at a voltage of 560V. The film was exposed to the ammonia plasma for one minute.

Next, the treated film was laminated with an adhesive and copper using a conventional nip roll method. Stacked material is made of copper 1oz, a layer of Pyralux ^(R) sheet adhesive of 1 mil, a strip of polyimide film, the other layer of copper 1oz of sheet adhesive and another layer of 1 mil, to form a clad.

To test the bond strength of the copper to the rest of the cladding, the copper was placed on the upper jaw of an Instron tester and the remaining cladding was adhered to a German wheel with double-sided adhesive tape. The wheel was rotated while copper was peeled at a strength to maintain a peel angle of 90 degrees. The pull rate was 2 in / min. Adhesion values and surface energies in pounds per inch (pli) of wire for control and ammonia plasma treated samples are listed below. Sample Adhesion Value (pli) Polar Surface Energy (Dyne / cm) Control 6.9 10.7 Ammonia Treatment 13.0 23.2 (Example 2) Increased Shielding Property against Poly (ethylene terephthalate) (PET) Film DuPont Co . 5 "x 5" M for sale from Wilmington, DE
YLINEX the ^(R) type S PET film, to oxygen permeation through the PET film, for providing a higher degree of shielding, for plasma thin film coating disposed between the assembly as described in Example 1. A vacuum was induced at a pressure of 150 mTorr. Acetylene was introduced into the room at a flow rate of 25 sccm, and power was supplied at a voltage of 640V. The film was exposed to the acetylene plasma for 10 minutes. The treated film was then subjected to OXT manufactured by Mocon, Inc. at 30 ° C. and 50% relative humidity (RH) according to ASTM D3985.
The use of RAN ^(R) 1000, oxygen transmission rate (OTR) (Oxyge
n Transmission Rate (Ox), also known as the Transmission Rate
ygen Permeation Rate). The results are as follows. Sample thickness (mils) OTR (cc / m ² / day) control 4.94 12.57 acetylene treatment 4.88 2.48

[Brief description of the drawings]

FIG. 1 is a drawing of one embodiment of a cathode assembly of the present invention showing a cell having a generally square cross-sectional configuration.

FIG. 2 is a drawing of one embodiment of the cathode assembly of the present invention, showing cells having a generally circular cross-sectional configuration.

FIG. 3 is a drawing of one embodiment of the cathode assembly of the present invention, showing the cell in the form of a generally parallelogram cross section.

FIG. 4 is a drawing of one embodiment of the cathode assembly of the present invention showing a cell having a generally triangular cross-sectional configuration.

FIG. 5 is a drawing of one embodiment of the cathode assembly of the present invention, showing a cell having a generally pentagonal cross-sectional configuration.

FIG. 6 is a drawing of one embodiment of the cathode assembly of the present invention, showing a cell having a generally elliptical cross-sectional configuration.

FIG. 7 is a drawing of one embodiment of the cathode assembly of the present invention, showing a cross section of a cell having a flat bottom end.

FIG. 8 is a drawing of one embodiment of a cathode assembly of the present invention, showing a cross section of a cell having various configurations as a distal end.

FIG. 9 is a drawing of one embodiment of a cathode assembly of the present invention, showing a cross section of a cell having various configurations as a distal end.

FIG. 10 is a drawing of one embodiment of a cathode assembly of the present invention showing cells in an array having a configuration adapted to process a substrate having the configuration.

FIG. 11 includes one including a dielectric material covering the wall, and the other including at least one dielectric material.
1 is a drawing of one embodiment of the plasma generator of the present invention, showing an assembly of two types of cathodes located adjacent to one cell. In addition, an apparatus for supplying a plasma precursor gas, a cathode assembly and an apparatus for supplying power to a substrate are shown.

FIG. 12 is a perspective cutaway view of one embodiment of the cathode assembly of the present invention adapted to process bottle-shaped containers.

FIG. 13 is a cross-sectional view of the embodiment of FIG.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] December 14, 2000 (200.12.14)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Contents of correction]

[Claims]

1. A hollow multiple electrically conductive in the array of arranged cylindrical surface of the cylinder plasma generating cell (the corresponding cell are electrically connected to each other), at least one of including apparatus for supplying the assembly of the cathode gas of the plasma precursor, and apparatus for supplying power to the assembly of the cathode, comprising the at least one cathode assembly for generating plasma, a A plasma generator.

2. The plasma generator of claim 1 wherein a precursor gas is provided adjacent to the cathode assembly, whereby the gas diffuses proximally of the cell.

3. Assembly of the cathode further comprises a manifold及 beauty one or more passageways in communication with the cell, is supplied to the assembly of the cathode gas precursor through said passage into said cell whereby gas you diffuse proximally of the cell, the plasma generator according to claim 1.

4. The plasma generator of claim 1 wherein the cells are arranged in a cylindrical array on the inner surface of the cylinder .

5. The plasma generator of claim 1 wherein the cells are arranged in a cylindrical array on the outer surface of the cylinder .

6. The method according to claim 1, wherein the plurality of cells are in the form of a cylindrical cross section or a regular or
2. The plasma generator of claim 1 having the form of an irregular polygonal cross section.

7. A plurality of cells, a triangle, a parallelogram, pentagonal, hexagonal, heptagonal shape, octagonal, and regular polygonal cross-section of a form selected combinations thereof, from the group consisting of The plasma generator of claim 1 having the following.

8. A plasma generator according to claim 1, wherein at least one surface of the substrate is located in close proximity to the at least one cathode assembly.
(B) supplying at least one gas in the plasma precursor proximate the cathode assembly and the substrate, thereby generating a plasma by supplying power to the assembly (c) a cathode, and (d) A method of treating at least one surface of a generally cylindrical substrate, comprising exposing at least one surface of the substrate to a plasma for a time sufficient to form a treated surface.

9. substrate is a polyimide, a method of claim 8.

10. The method of claim 8, wherein the substrate is a polyester.

11. substrates is a polyester chosen from a copolymer of polyethylene terephthalate homopolymer or ethylene terephthalate, wherein up to about 50 mole percent of the copolymer, in the preparation of the copolymer, the grayed recall portion substituted for, diethylene glycol, propane-1,3-diol, butane-1,4-diol, polytetramethylene glycol, polyethylene Ji glycol, polypropylene glycol and 1,4-hydroxymethyl cyclo hexane or, copolymers substituted acid moiety in the preparation, isophthalic acid, bibenzoic acid, naphthalene 1,4- or 2,6-dicarboxylic acid, adipic acid, sebacic acid, and decane-1,10-dicarboxylic acid, the 9. The composition of claim 8, prepared from monomer units. the method of.

12. The method of claim 11, wherein the substrate is a container of biaxially oriented poly (ethylene) terephthalate .

13. (a) forming a container molded biaxially oriented polyester, (b) using the assembly of the cathode of the plasma generator according to claim 1, the plasma precursor comprising hydrocarbons a plasma generated from a gas, exposing the least 1 surface of the container, introducing a liquid into (c) a container, comprising a, to seal (d) is a container, the molded biaxially oriented A method for filling a liquid into a generally cylindrical container of polyester .

14. The method of claim 13, further comprising expelling a plasma precursor gas from the vessel prior to introducing the liquid .

15. using the assembly of the cathode of the plasma generator according to claim 1, the plasma generated from a gas plasma precursor comprising hydrocarbons, exposing at least one surface of the polyester substrate, comprising a way of reducing the gas permeability of the generally cylindrical polyester substrate.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Contents of correction]

[0008] EP 634 778 describes an array of hollow cathodes that generate a plasma for surface etching and removal of "rolling oil" on metal sheets. The hollow cathode array system comprises a housing having a plurality of openings uniformly spaced along one wall of the housing. The hollow cathode plasma is basically generated in the housing and transported through the opening. Such an array of openings acts as a distributor but does not increase plasma intensity and uniformity. Each opening has a diameter of about 1/16 inch (0.15 cm). The pressure used in the system of EP 634 778 is in the range of 0.1 to 5.0 torr (13.33 to 666.61 Pascal) and the applied power is 0. Between 0.5 and 3.0 kW.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Contents of correction]

US Pat. No. 5,686,789 describes a discharge device having a cathode with a fine hollow array for use in subminiature fluorescent lamps. This patent covers devices with dimensions of the mean free path magnitude of electrons that cannot be performed for large area processing. The electrons undergo an oscillating motion within the fine hollow, which results in a fine hollow discharge, increasing the current capability. US Patent 5,6
The 86,789 system uses a pressure of 0.1 Torr to 200 Torr ( 13.33 to 26,664.48 Pascals) in use. The patent does not mention reactive plasma, plasma polymerization, or surface modification of materials.

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A low pressure (in vacuum) is used for the plasma processing of the present invention. Therefore, the present invention
The plasma generator further includes a vacuum chamber in which the cathode assembly fits, and a vacuum.
Comprising an apparatus for providing. Suitable as a cylindrical stainless steel vacuum chamber
A suitable vacuum chamber has been found to be appropriate. Edwards High Vacuu
m Times such as E2M80 / EH500 from International
Use a commercial vacuum pump that includes a booster pump in combination with a transfer pump
can do. Pressures useful in the present invention range from about 1 mTorr to about 100 Torr. (0.1333 to 13,332.24 Pascal) , Preferably 1 millitorr
Or about 1 tall(0.1333 to 133.32 Pascal)In the range of
Can be. Batch or continuous when using the plasma generator or method of the present invention
Processing is possible. Vacuum systems tend to lend themselves to batch processing
However, by using a step-linked vacuum system, continuous processing can be performed at sub-atmospheric pressure.
Can be maintained. A series of chambers under a differential pressure can be created using the "step-linked vacuum
means.

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[0045]

EXAMPLES Example 1 Increase in Adhesion of Polyimide Film to Copper Two types of 12-in.times.12 having a square cell pattern similar to that shown in FIG.
An in (30.48 cm × 30.48 cm) cathode assembly was manufactured from stainless steel. Each cell had a measurement of 1 in x 1 in x 1 in (2.54 cm x 2.54 cm x 2.54 cm) and the ratio of cell cross-sectional area to cell depth was equal to 1.0. The two cathode assemblies were placed parallel to each other in a vacuum chamber, and each cathode was connected to a DC power supply. E. FIG. I. Du Pont d
e A Kapton® polyimide film, available from Nemours and Company, Wilmington, DE, is approximately 2 inches (5.08 inches ⁾ from each cathode.
cm) between the cathodes. Vacuum was introduced at a pressure of 150 mTorr. Ammonia was introduced into the room at a flow rate of 12 standard cubic centimeters (sccm) per minute and was powered at a voltage of 560V. The film was exposed to the ammonia plasma for one minute.

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Next, the treated film was laminated with an adhesive and copper using a conventional nip roll method. Stacked material is copper 1oz (28.34 grams), a layer of Pyralux ^(R) sheet adhesive of 1mil (0.0254 mm), strips of polyimide film, the other layer of the sheet adhesive and another layer of 1mil It consisted of 1 oz of copper ( 28.34 grams) and formed the cladding.

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To test the bond strength of the copper to the remaining cladding, the copper was subjected to an Instron test.
Place the rest of the clad on the upper jaw of the
Glued. While peeling copper at a strength that maintains a peel angle of 90 degrees,
Rotated. The pulling speed was 2 in / min (5.08 cm / min). Control
Per inch of wire (pli) for ammonia and ammonia plasma treated samples (Newton / meter (N / m)) The adhesion value and surface energy of
Can besample Adhesion value (pli) (N / m) Polar surface energy(Dyne / cm) Control 6.9(1208.19) 10.7 Ammonia treatment 13.0(2267.3) 23.2 (Example 2)Increased shielding properties for poly (ethylene terephthalate) (PET) films DuPont Co. 5 "x 5" for sale from Wilmington, DE( 12.7cm × 12.7cm) MYLINEX^(R)type S PET Fill
To provide a higher degree of shielding against oxygen transmission through the PET film
During assembly as described in Example 1 for thin film coating of the plasma.
Placed. A vacuum was induced at a pressure of 150 mTorr. At a flow rate of 25 sccm
Cetylene was introduced into the room and power was supplied at a voltage of 640V. Assemble the film
Exposure to Tylene plasma for 10 minutes. Next, the treated film is treated at 30 ° C. for 5 minutes.
At 0% relative humidity (RH), according to ASTM D3985, Mocon,
OXTRAN manufactured by Inc.^(R)By using 1000
Elemental transmittance (OTR) (Oxygen Transmission Rate)
Oxygen Permeation Rate
Was evaluated. The results are as follows.sample Thickness (mils) (Mm) OTR (cc / m ² / day) Control 4.940.125 12.57 Acetylene treatment 4.880.124 2.48

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) // C08L 67:00 C08L 67:00 79:00 79:00 Z (81) Designated country EP (AT, BE) , CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA , GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AU, BA, BB, BG, BR, CA, CN, CR, CU, CZ, DM, EE, GD, GE, HR, U, ID, IL, IN, IS, JP, KP, KR, LC, LK, LR, LT, LV, MG, MK, MN, MX, NO, NZ, PL, RO, SG, SI, SK, SL , TR, TT, UA, US, UZ, VN, YU, ZA (72) Inventor Lynn, Theo-Gene, 1917, Tazford Rotherfield Lane, Pennsylvania, USA 910 F-term (reference) 4F073 AA17 BA23 BA31 BB03 CA01 CA07 DA08 4G075 AA30 AA62 BA05 BA06 BD14 CA47 CA62 CA63 EC21 EE02 EE05 FA05 FC15

Claims (31)

[Claims] 1. A cathode assembly for generating a plasma, comprising a plurality of electrically conductive hollow plasma generating cells in an array, wherein the cells are electrically connected to each other. 2. The cathode assembly of claim 1, wherein the ratio of the area of the cell cross section to the cell depth is in the range of about 0.1 to about 5.0. 3. The cathode assembly of claim 2, wherein the cross-sectional area of the cell ranges from about 1.6 to about 64.5 cm ² . 4. The cathode assembly of claim 1, wherein adjacent cells share at least one common wall. 5. The cathode assembly of claim 1, wherein the plurality of cells are separated from at least one adjacent cell. 6. The cathode assembly of claim 1, wherein at least one wall of at least one cell is coated with a dielectric material. 7. The assembly of claim 1, wherein the dielectric material is disposed adjacent to at least one cell. 8. The method of claim 1, wherein the plurality of cells have a generally circular cross-sectional configuration.
Cathode assembly. 9. The cathode assembly of claim 1, wherein the plurality of cells have a generally elliptical cross-sectional configuration. 10. The cathode assembly of claim 1, wherein the plurality of cells have the form of a regular or irregular polygonal cross section. 11. The plurality of cells has a regular polygonal cross-sectional form selected from the group consisting of triangles, parallelograms, pentagons, hexagons, heptagons, octagons, and combinations thereof. The assembly of the cathode of claim 10. 12. The cathode assembly of claim 10, wherein the plurality of cells have the shape of an irregular polygonal cross section, said shapes being the same or different. 13. The cathode assembly of claim 1, wherein at least some of the cells adjacent to the periphery of the array have a smaller cross-section than cells inside the array. 14. The cathode assembly of claim 1, wherein the cells are arranged in a generally planar array. 15. The cathode assembly of claim 14, wherein each cell has at least one wall substantially perpendicular to the plane of the array. 16. The cathode assembly of claim 14, wherein each cell has at least one wall forming an obtuse angle with the plane of the array. 17. The cathode assembly of claim 14, further comprising a planar base, wherein the discussion cell is mounted on the base. 18. The assembly of claim 1, wherein the cells are arranged in an array having a shape. 19. The cathode assembly of claim 18, wherein the array having the shape is concave. 20. The cathode assembly of claim 18, wherein the shaped array is convex. 21. An assembly of at least one of the cathodes of claim 1, an apparatus for supplying a gas of a plasma precursor to the assembly of at least one cathode, and an apparatus for powering the assembly of cathodes A plasma generator, comprising: 22. The plasma generator of claim 21, wherein a precursor gas is provided adjacent to an assembly of cathodes whereby the gas diffuses proximally of the cell. 23. (a) disposing at least one surface of a substrate proximate to the at least one type of cathode assembly of claim 1; (b) proximate to the cathode assembly and substrate. Supplying a gas of at least one plasma precursor; (c) generating a plasma by supplying power to the cathode assembly; and (d) a time sufficient to form a treated surface. Exposing at least one surface of the substrate to a plasma, the method comprising treating at least one surface of the substrate. 24. The method of claim 23, wherein the substrate is a polyimide. 25. The method of claim 23, wherein the substrate is a polyester. 26. The substrate is a polyester selected from a polyethylene terephthalate homopolymer or a copolymer of ethylene terephthalate, wherein up to about 50 mole percent of the copolymer, based on the glycol moiety, Substituted diethylene glycol, propane-1,3-
Diol, butane-1,4-diol, polytetramethylene glycol, polyethylene glycol, polypropylene glycol and 1,4-hydroxymethylcyclohexane, or isophthalic acid, dibenzoic acid, naphthalene substituted by an acid part in the preparation of a copolymer 24. The method of claim 23, prepared from monomer units of 1,4- or 2,6-dicarboxylic acid, adipic acid, sebacic acid, and decane-1,10-dicarboxylic acid. 27. The method of claim 26, wherein the substrate is a bottle of biaxially oriented poly (ethylene) terephthalate. 28. The method of claim 27, wherein the plasma precursor gas comprises acetylene. 29. A plasma precursor comprising a hydrocarbon using the cathode assembly of claim 1 wherein: (a) forming a container of molded biaxially oriented polymer; (b) the array is in the form. Exposing at least one surface of the container to a plasma generated from the gas of (c), (c) introducing a liquid into the container, (d) sealing the container, comprising: A method for filling a liquid inside. 30. The method of claim 28, further comprising expelling a plasma precursor gas from the vessel prior to introducing the liquid. 31. Exposing at least one surface of the polyester substrate to a plasma generated from a gas of a plasma precursor comprising a hydrocarbon using the cathode assembly of claim 1. A method of reducing the gas permeability of a polyester substrate.