TW200827469A - Improved plasma-enhanced chemical vapor deposition coating process - Google Patents

Abstract

A process for coating or modifying a substrate using plasma-enhanced chemical vapor deposition (PECVD) is described in which a plasma is generated in a gaseous mixture containing at least 35 volume-percent nitrogen gas, at least 50 ppm of least one gaseous silicon-containing compound, and up a 1.5:1 volume ratio of at least rare gas relative to nitrogen gas, the rare gas comprising at least 1 volume-percent helium gas, at least 1 volume-percent neon gas, or at least 3 volume-percent argon gas, each volume-percent based on the total volume of the gaseous mixture at 20 DEG C and 101 kPa pressure. This process is capable of producing coatings which are monolithic and substantially uniform at high deposition rates and/or low power density. The process is useful for making a surface modified coating such as an adhesion promoter or an antifog coating; an optical coating such as a reflective or antireflective coating, a light spectrum management coating. or UV protection coating; a chemical resistant coating; an abrasion-resistant coating; or a gas barrier coating. Examples of potential end use applications include online coating of extruded plastic film, sheet, laminates and molded articles useful in architectural glazing, glazing panels, solar collectors, appliances, optical consumer products and devices, packaging, signage, and transportation.

Description

。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 BACKGROUND OF THE INVENTION This invention relates to the coating or upgrading of a substrate by plasma enhanced chemical vapor deposition (PECVD). [Prior Art 3

It is known to coat substrates with PECVD. US-A-5, 718.967, WO 10 03/066932 and US-A-6,815,014 describe the use of PECVD for the coating of organic stone. WO 2005/049228 describes an application for coating a corrosive stone with PECVD. W〇2〇〇5/113856 describes an application for coating non-shixi metal oxides by PECVD. The substrate can be a plastic material. In this art, various solutions have been proposed for how to obtain a commercially acceptable wealth or shisha soil coated with PECVD on various substrates under atmospheric pressure. However, this technique has not yet been found to be suitable for obtaining a solution that is suitable for high readability and optical penetration at high deposition rates. In particular, this (4) has not yet found a problem of how to reduce the amount of money and rare industrial waste gas (e.g., helium) while obtaining high-quality _cvd paint. The invention described below can be expected to solve the problem of depositing ruthenium-containing materials with _Mpecvd. SUMMARY OF THE INVENTION 5 200827469 SUMMARY OF THE INVENTION The present invention provides a method for coating or modifying a substrate comprising: (a) providing a substrate having at least one surface; 5 (b) providing a gas mixture , at least one surface adjacent to the substrate of (a); (c) producing a plasma in the gas mixture in (b), and (d) allowing the plasma in (c) to be on at least one surface of the substrate Forming a solid deposit, 10 wherein the gas mixture comprises: at least 35 vol% nitrogen at 20 ° C and 101 kPa pressure (based on the total volume of the gas mixture); at least 50 ppm of at least one gas precursor is used to form the Solid deposition; and at least one rare gas and nitrogen 15 gas having a volume ratio of at most 1.5:1, the rare gas comprising at least 1% by volume of helium, at least 1% by volume of helium, or at least 3% by volume of argon, each volume% The total volume of the gas mixture at 20 ° C and 101 kPa pressure is used. The present invention also provides a coated or modified base 20 by the above method. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a reproduction of a scanning electron microscope (SEM) image showing the surface morphology of a polycarbonate substrate coated in Comparative Example 2 as described below. 0 6 200827469 Fig. 2 An SEM image was reproduced which shows the surface morphology of the polycarbonate substrate coated in Comparative Example 1 as described below. Fig. 3 is a reproduction SEM image showing the surface morphology of the polycarbonate substrate coated in Example 5 as described below. C embodiment] Detailed description of the preferred embodiment

For the purposes of US patent practice, any patent content, patent application, or publication referred to herein is hereby incorporated by reference in its entirety, or in its entirety in the U.S. Among them, in particular, the disclosure, raw materials and common sense of the synthesis technology in the technique of the present invention. All "parts" and "%" are by weight unless otherwise stated or in the context of the context or in accordance with the teachings of the art. The words "including," and their derivatives are used in this document to exclude the existence of any other group injury, step, or procedure, whether or not the same is disclosed herein. 15 In order to avoid any doubt, unless otherwise stated, all The composition may include any additional additives, adjuvants or compounds by the use of the term "include. Conversely, where the term "substantially consists of" is used herein, the scope of any other components, steps, or procedures described in the following is excluded, except those that are not necessary for operability. If the term "consisting of" is used, exclude any components, steps or procedures not specifically stated or listed. Unless otherwise stated, any combination is used. Otherwise, the term "or, is a list of Each member or its nitrogen as used herein may be a component of nitrogen or itself. As used herein, "oxidizing gas" means a gas that at least - oxidizes at least - the former 200827469-5 drive. The term "gas precursor" means at least one gaseous reactive species that forms a solid deposit on a substrate under conditions of PECVD. As used herein, "blunt gas" refers to other components that are not mixed with a gas. The gas of reaction and the gas mixture forms a covalent compound with other components in the plasma state. An "blunt gas" does not include an oxidizing gas or a gas precursor. Examples include nitrogen, argon, carbon dioxide gas, helium gas and Helium. Unless otherwise stated, the terms "liter" and "cubic centimeter" (cc) refer to a specific gas or gas mixture body 10 at ambient temperature and large gas pressure. Unless otherwise stated herein, the term "slpm" means "standard liters per minute" and means that the body flow rate is converted to liters per minute at standard temperature and pressure. Unless otherwise stated herein, the term "seem" Represents “standard cubic centimeter 15 / min” and means that the gas flow rate is converted to ± centimeters per minute at standard temperature and pressure. Unless otherwise stated herein, the term “volume %” refers to the total volume of the gas mixture. The amount of gas or gas mixture. As used herein, the volume % values and ranges correspond to the respective gases of the total pressure of the gas mixture. The pressure is expressed as %. As used herein, the ambient temperature means about 21°. Temperature of C. As used herein, standard temperature refers to a temperature of 〇 ° C. As used herein, large gas pressure refers to the atmospheric pressure of a horizon, typically about 101 kPa of sea level.

"Frequency" means a cycle of several applied voltages or charges per second and then back to the minimum again, as defined herein, "frequency flow from minimum to maximum 10 HerzOIz" (ie, cycles per second) frequency). The voltage of the helper electrode. As used herein, "applied voltage," means a metal oxide applied to an electrode or a metal oxide, "metal oxide," which means that the compound contains at least a knot, including a polymeric metal containing less than a stoichiometric amount of oxygen. Things. 15 The term "organometallic compound" means a metal-containing and/or a plurality of bonds or permeations directly with a metal or a plurality of oxygen atoms bonded to a metal bond by an aliphatic "oxoaliphatic or halogen family The term "cerium oxide" means that the compound contains at least some of the oxygen bonds including polymeric cerium oxide, which contains less than one stoichiometric amount of oxygen. 20 The term "organic cerium compound, means cerium and direct A compound that binds to one or more aliphatic or cycloaliphatic steroids through one or more oxygen or nitrogen atoms through a bond with a hydrazone bond. It should be understood that the chemical formula of the metal oxides, organometallic compounds, cerium oxides and organic cerium compounds prepared herein is 9 200827469. The experimental formula is not a molecular formula. As used herein, the term "integral" means that a solid layer is substantially free of cracks and potholes. It is highly desirable that the solid does not have a deformation extension of greater than 10% of the thickness of the solid layer from the surface. By means of a solid layer having a maximum thickness of greater than or equal to 8% by weight and a deformation extension of no more than 25% of the thickness of the solid layer from the surface. Using m back adhesive or 'adhesive layer, refers to an organic stone film deposited on an organic polymeric substrate, which can be combined with a metal oxide surface layer, and the layer is formed with When the distance between the surface of the rolling water is 曝Q em exposed to the boiling water for at least 3 minutes (preferably 10 minutes), the anti-condensation property is not lost, and the surface of the substrate is detached. It is highly desirable that the organic polymeric substrate comprises a polymer. Carbonate, polyolefin or polyacrylate polymer. As used herein, the term 'film' means any desired length or width and has a thickness of 15 (1) but not including 0.1 cm. Substrate. As used herein, a "sheet" means that the substrate Gf has any desired length or width and has a thickness of from 0.1 to 10 cm. The gas mixture may be any gas mixture as defined above and is subjected to PECVD. A deposit may be formed on the substrate during processing. Preferably, the deposit comprises at least one macromolecule and more preferably at least one polymer. The gas mixture comprises nitrogen, at least a gas precursor, a rare gas - a rare gas And optionally comprising at least one oxidizing gas. The gas mixture comprises at least 35% by volume of nitrogen, preferably at least a shirt body of 200827469%, preferably at least 555% by volume, preferably at least 65% by volume. And preferably at least 75% by volume (based on the total volume of the gas mixture at a pressure of 20 ° C and 1 〇 1 kPa). The volume ratio of the rare gas to nitrogen is not more than 1 · 5. · 1, Large • 5 is preferably 1:1, more preferably no more than 1: 2, no more than 1 · · 4 is better - and no more than 1 · · 5 is especially good (with the gas mixture at 20 Total volume at °C and 101 kPa pressure). A large amount of each rare gas is preferably not more than 37% by volume, more preferably not more than 20% by volume and preferably not more than 10% by volume (by the gas 10 mixture at 20 ° C and 101 kPa pressure) The total volume is: at least 1% by volume, preferably at least 2 and more preferably at least 3% by volume (to the total volume of the gas mixture at 2 (rc & 1 kPa pressure) Alternatively, the amount of helium is preferably at least 1% by volume, more preferably at least 2% by volume 15 and preferably at least 3% by volume (by the gas mixture at a pressure of, for example, 101 kPa) Total volume) 3, the amount of nitrogen is preferably at least 3 vol%, preferably at least 1 vol% and more preferably 15 _% (with the gas mixture at 2 〇 ^ and 101 kPa pressure) The total volume is below.) 20 The above range is applicable to each of 氦, 氖 and argon (that is, the only one of 氦, 氖 or argon in the gas mixture falls in the basin) In the range, the amount range is met. In a preferred embodiment, the amount of gas present in the gas mixture Examples of suitable oxidizing gases in one or more of the above-mentioned preferred embodiments for use in the atmosphere include oxygen, nitrous oxide (N20), ozone (03), nitrogen monoxide (N〇), and tetra-oxidation. Dinitrogen, and combinations thereof, may be added by itself or as a component of a gas. When a macromolecule or polymer is desired, the amount of the oxidizing gas in the gas mixture is at least 1 volume. % is more preferably at least 5% by volume, more preferably at least 10% by volume and even more preferably at least 15% by volume (based on the total volume of the gas mixture at a pressure of 20 ° C and 101 kPa) . Preferably, the ratio of the precursor to the oxidizing gas is at least 2.5 X 1 〇·4 and more preferably at least 1.25 X 10 , and most preferably 〇·〇5 and not more than 〇 〇3. 10 The gas mixture may be free of oxidizing gas or a low concentration of oxidizing gas, for example less than 1% by volume, more preferably less than 01% by volume, and preferably less than 0.001% by volume (by the gas mixture) At a total volume of 2 Torr and a pressure of 1 〇 1 kPa, it is most desirable to have substantially no oxidizing gas to obtain a substrate having the above adhesive coating, such as w〇2〇〇6/〇 36461 and 15 WO 2006/049794. The method of the present invention can be used to produce a substrate having a multilayer coating comprising at least one macromolecule or polymeric layer and at least one adhesive layer as described in WO 2006/036461. The method of the present invention can be used to produce a substrate having a coating comprising at least one metal oxide layer as described in the embodiment of WO 2005/113856. The ratio of the ratio of the oxidizing gas to the passive gas is preferably in the range from 0 to 3:1 Torr. The preferred rate ratio includes the minimum value of 〖: 别: 〇 and the maximum ratio is 1: 10 and 1: 50. The preferred range and sub-range include all possible combinations of the aforementioned 12 200827469 咼 low boundary values. The gas precursor may or may not be a gas at ambient temperature and high gas pressure. When the gas precursor is not a gas at ambient temperature and large gas pressure, the 5 precursor may be evaporated by heat, agitation, charging, microwave energy and/or vacuum to cause the precursor and the blunt gas and any oxidation. Gas group • Combined. A well-known device that can be used to vaporize one or more non-gas precursors to form a gas precursor and combine it with other gases is a controlled evaporative mixer. In a preferred embodiment, at least one precursor is mixed with helium before the precursor is added to the other components of the gas mixture. In a specific embodiment, the precursor is added by a helium gas through the precursor while the precursor is agitated or heated. Preferably, at least one macromolecule and/or at least one polymer is formed when the precursor is subjected to PECVD treatment. When the gas precursor is a ruthenium compound, it is preferred that the precursor form an organic ruthenium or oxidized smectite in the case of PECVD. When the gas precursor is at least one metal-containing compound, it is preferred that the precursor be formed into a metal oxide in the case of PECVD. Examples of precursors suitable for use in the manufacture of organic cerium or cerium oxide deposits include cerium-containing compounds such as decane, decane and decazane. Preferably, the ruthenium containing compound can be represented by the formula (I): • R3Si[X-Si(R')2]rR" (1) wherein each of R, R, and R" represents 屮, 〇H, and Gw. a hydrocarbyl group' or a Ci-io-based oxy group; X represents, where R,,,, 13 200827469 ▲ each occurrence of each represents a Cii 〇 hydrocarbon group and r represents 〇 or a range of To the value of ίο. The hydrocarbyl and alkoxy groups may be saturated or unsaturated, substituted or unsubstituted, and branched or unbranched. Preferably, the cerium compound-containing organic cerium compound is preferred and at least one (preferably at least 5, preferably) Cl_1G hydrocarbon group is preferred and/or at least one (at least three is preferred) Alkoxy groups. It is preferred to include up to three carbon atoms in each of the muscle-1() hydrocarbyl groups. Examples of the materials include dimethoxydimethyl Wei, methyl trimethyl. Alkane, tetramethoxy decane, methyl triethoxy decane, diethoxy dimethyl decane, 10 methyl diethoxy sulphate, triethoxy ethene, tetraethylene oxime (also known as Sizheng Shixi) Ethyl acetate or TEOS), dimethoxytolyl-based sulphur, phenyltrimethicone, 3, methyltriethylphosphonium trimethoxy sulphate 9, 3-methyl propylene propyl propyl; Burning, diethoxymethyl stupid, tris(2_曱oxyethoxy) ethoxylate Shixi, stupid triethoxylate and dimethoxydiphenyl sulphide. 15 oxirane example Including tetramethyldioxane (TMDSO), hexylmethyloxane (HMDSO), and octyl-trioxane. Examples of decazane include hexylmethyl decazane and tetradecyl quinone. These precursors It can be used to make deposits or coatings containing: polymeric cerium, polymeric siloxanes and/or cerium oxide, depending on the starting material and the amount of oxidizing gas present. The presence of low or zero oxidizing gases can be utilized. Production of polymeric organic germanium deposits or coatings, particularly when the precursor comprises decane or decane. Increasing the concentration of oxidizing gas enhances the manufacture of polyoxane or cerium oxide deposits or coatings. Suitable precursors for the manufacture of metal oxide deposits Examples include 14 200827469, metal compounds such as yl, oxyi or yttrium, tin, Cui § and chin. Preferred metal-containing compounds can be represented by the formula (Π): MRaXb (II) wherein Μ represents Zn, a metal of Sn, A1 and Ti; when R' is respectively present, - 5 represents -H, -OH, a hydrocarbyl group or a Ci, an alkoxy group; X generation; Table 1 halogen, including C1 or Br; "a" and "b" each represent an integer of the R and X moieties, as previously described 'in the range from 0 to the 1 valence. Let the total number of a+b be equal to the valence of the metal ruthenium; or Volatile salt. Suitable for metal oxides such as flooding examples include Ethyl, dimethyl 10 zinc, zinc acetate, titanium tetrachloride, tin dimethyl diacetate, zinc acetylacetonate, zirconium hexafluoroacetate, zinc carbamate, trimethyl indium, triethyl indium , (2,2,6,6-tetramethyl-3,5-heptanedionate) ruthenium (IV) and mixtures thereof, etc. Metal oxide examples include zinc, bismuth, titanium, indium bismuth and a mixture of oxides and the like. 15 It is desirable for the precursor to be present in the gas mixture in the range of 5 〇 ppm, preferably at least 200 ppm and at least 5 〇〇 ppm to not more than 10,000. The ppm is more preferably not more than 8,000 ppm and more preferably not more than 7000 ppm. A preferred embodiment of the gas mixture is a mixture of a precursor and air 20, wherein the concentration of the precursor compound is preferably in the range of one or more of the foregoing precursor concentrations. It is preferred to adjust the flow rate and concentration to obtain an average thickness of the coating on a substrate of not more than 5 μηι, more preferably not more than 2 μηη, more preferably not more than 为·1 μηι and more preferably At least 1 nm is preferred. Preferably, at least 15 200827469 10 nm is more preferred and at least 3 〇 11111 is preferred and the thickness relative to the average thickness is not more than Ιμηι, preferably not more than 5 ηηι and not more than Ο.ΐμτη. It is preferable that the thickness is not more than 刈% with respect to the thickness of the average thickness, more preferably not more than 20%, and still more preferably not more than 1%. 5 It is preferred to produce a stable plasma by the volume of the gas mixture to uniformly deposit the polymerization product. Preferably, the volume of the gas mixture above the substrate is at least about 0. 05 m/s. It is preferably at least about 〇j m/s and preferably at least about 0.2 m/s; and preferably not more than about 1 〇〇〇 m/s. It is preferably not more than about 500 m/s, and preferably not more than about 2 〇〇 m/s. Preferably, the volumetric flow of the gas mixture exposed to a plasma of 10 to the surface area of the crucible is from 10 to 1,500 CC/min per square centimeter. Preferably, the pressure of the gas mixture added in step (b) is about 丨〇丨kpa + eight 20 kPa, for example at about a large gas pressure and a temperature of about 2 (rc+/_3 〇 it, such as ambient temperature. 15 The pressure of the gas mixture added in the step (b) is preferably higher than the pressure of the large gas from the range of IPa to 80 kPa. The pressure at which one of the gas mixture is added is greater than the pressure of the large gas to obtain the desired electrode. Gas lanthanum is preferred. The substrate is not limited to the substrate used in the present invention. Examples of the substrate include glass, metal, ceramic, paper, fiber, and plastic, such as polyolefin, including polyethylene and poly. Propylene, polystyrene, polycarbonate, and agglomerates, spooned polyethylene terephthalate and polybutylene terephthalate. In a preferred embodiment, the substrate for use in the present invention includes Cooking Hezhong 16 200827469 - Organic polymer of the formula. The substrate examples include films, sheets, fibers and woven or non-woven fibers of thermoplastic plastics, such as polyalkylene hydrocarbons, including polyethylene, polypropylene and ethylene, propylene and/or Or Cqa-dilute hydrocarbons, polystyrene The copolymerization mixture, the polyacetic acid vinegar, the polyester vinegar, including the polyethylene diacetate benzoic acid vinegar, the polylactic acid-5 vinegar and the polybutylene terephthalate vinegar, the polyacrylic acid S, the polyfluorene acrylate, and the use thereof An interpolymer of any of the foregoing polymers. The organic polymeric substrate of the present invention may comprise one or more layers and have a first and a second surface. The first of the organic polymeric substrates of the method of the invention / or ^ The second surface can be coated. The coated substrate herein refers to a composite 10. The preferred substrate is a polycarbonate. It should be understood that the foregoing structure may comprise one or more layers of the same or different a layer of organic polymer 'and any other suitable material, such as wood, paper, metal, cloth or one or more metal oxides or metalloids, such as terracotta, talc, alumina, alumina, Tantalum nitride or stone, as one or more layers of a multilayer 15 structure or as a component of one or more layers, if the exposed surface of the substrate comprises one or more organic polymers. Any of the techniques may be used. Method of making a layer, such as, but not limited to Coextruded, heat sealed, layered with an adhesive and the like. A preferred layer comprises a polycarbonate sheet and a polycarbonate film, wherein the polycarbonate comprises a UV* a film of 20 received. A further preferred layer is a polycarbonate sheet having a first surface and a second surface, wherein a polycarbonate film comprising a UV absorber is laminated to the film. a first and a second surface of the carbonate sheet; the polycarbonate film may have the same or different composition. Alternatively, the film comprising the UV absorber is a poly(meth)acrylate. Preferably, in a method of 17 200827469, the uv absorber is grafted, copolymerized or otherwise bonded to the organic polymer. The plasma produces any useful material for producing a plasma in step (c). Suitable device embodiment package

- 5 includes US 5,433,786, WO 2003/066932, WO 2003/066933, WO-2005/049228, Ward et al, Langmuir, 2003 19, 2110-21 14 and other devices described. In all of the foregoing devices, the precursor is supplied to the flowing gas stream (carrier gas) in the vicinity of the electrode in the form of a vapor, preferably by passing or passing through the surface of the electrode, wherein a plasma is applied to the electrode and One auxiliary 10 between the electrodes. Heating may be used to increase its vapor body pressure or to increase the amount of precursor by means of an atomizer', e.g., an ultrasonic atomizer. The method for achieving sufficient pressure of the precursor vapor body is preferred because the temperature rise is prevented from approaching the temperature of the auto-ignition gas mixture. Although the method is operated at atmospheric pressure, it should be understood that the pressure is higher or lower than atmospheric pressure (20 15 kpa). Preferably, the operating pressure is atmospheric pressure or greater than the large gas pressure Φ force is sufficient to obtain the desired gas flow through the electrode as desired. Embodiments of the above-described suitable apparatus include means for generating a plasma discharge via plasma, such as a dielectric shield discharge device. Such devices include one or more electrodes and/or a plurality of auxiliary electrodes and have a voltage applied between the electrodes 20 and the auxiliary electrodes. The plasma is produced by discharging between the electrode and the auxiliary electrode.

The dielectric screen discharge is also referred to as "silent discharge" and "atmosphere-pressure_glow discharge." The dielectric barrier discharge is used as described in US-A-5,718,967, WO 03/066932, and US-A-6,815,014. PECVD Fabrication of an Organic 18 200827469 矽 Coating. Dielectric Shielding Discharge is used to fabricate a dioxide dioxide coating via PECVD as described in w〇2〇〇5/〇 49928. Dielectric shielding discharge is used as described in WO 2005 A metal oxide coating is produced by PECVD of /113856. The method of the present invention applies a sufficient power concentration and frequency to an electrode and/or an auxiliary electrode to create and maintain a glow discharge of a gas mixture located in the electrode and auxiliary electrode spacing. The power concentration (according to the surface area of the electrode exposed to the electropolymerization) is preferably at least w5 w/cm 2 , more preferably at least 1 w/·2, and most preferably at least 9 w/cm 2 , and It is preferably not more than 370 WW, more preferably not more than 14 〇 w/cm 2 and most preferably not more than 4 〇 10 W/cm 2 . The current applied to the electrode may be from 1 〇 to 1 〇, _ 瓦Set, from 100 to 1 〇 00 volts for 1 〇 to 5 〇〇 (8) volts for it to think lUGG 2G'GGG volts. The frequency is preferably at least 2, more preferably at least 5 kHz and at least 1 cell is preferred; and preferably no more than 100 kHz is optimal, and no more than 6 〇 It is preferred to be better than 15 and greater than 40 kHz. In order to obtain an effective power-to-plasma conversion, it is preferred to select the same frequency as the resonant frequency of the electrode auxiliary electrode configuration. The resonant frequency is equal to 2ττνΛ The reverse conversion of (ί. C), in which the L-type inductor is almost completely provided by the high-voltage terminal of the transformer; the AC-based capacitance is almost exclusively provided by the coating station = the electrode of the ship. Mainly by the transformer It is preferred that the high side voltage provides an inductance and that the capacitance is provided primarily by an auxiliary electrode ground configuration. Preferably, the embodiment applies power to the electrode; and the auxiliary electrode is grounded (ie, via the electrical conductor) In the specific embodiment 19 200827469, the voltage applied to the electrode is preferably applied at a fixed frequency with a minimum voltage value and a maximum voltage value. Relative to the maximum voltage is - Positive value And - the cycle between negative values, with the maximum voltage value being positive or negative in each cycle. • 5 The spacing between the electrode and the auxiliary electrode is sufficient to achieve and maintain a visible electro-plasma (glow) Preferably, the discharge is preferably at least 〇1 mm, more preferably at least 1 mm, and preferably not more than 5 〇 mm, more preferably not more than 2 〇 111111, and φ M is not more than 10 faces. Preferably, if necessary, the electrode, the auxiliary electrode or the material and the lion electrode may (4) have a dielectric sleeve f. In a specific embodiment, the electrode and auxiliary electrode pairs are attached to a high temperature resistant dielectric (e.g., ceramic). The substrate to be coated may be supported or transported or supported adjacent to the plasma to be intimately contacted or impacted by at least a portion of the substrate and the auxiliary electrode. The flow of the gas mixture and the encapsulation generated in the vicinity of the electrode cause the plasma polymer product to deposit on the surface of the substrate attached to the auxiliary electrode or to the vicinity of the pair of the package. A suitable gap is provided between the substrate and the electrode or the electrode for discharging the carrier gas, by-products, and unattached product - ^ ° to adjust the gap width to prevent excessive amounts of contaminated gas. Preferably, the electrode and the auxiliary electrode are located within 4 mm of the surface of the substrate, and more preferably 20 within 1 mm. Any suitable electrode geometry and reactor design can be used in this month's method. For thick substrates, such as sheet materials, it is desirable for the electrode and the auxiliary electrode to be on the same side of the substrate to be coated. The reaction product is impacted on the surface of the substrate by means of an electrode attached post-electrode. The reactor excludes the pores 20 200827469 from the surface of the substrate and is removed from the electrode in terms of space before leaving the reactor to allow plasma or at least to form The reactants in between are in contact with the surface of the substrate. If desired, the shape of the resulting corona discharge can be modified by a magnetic field. For a thinner substrate, the auxiliary electrode can be a conductive surface on which it is carried. There is a target or substrate. The substrate or the entire auxiliary electrode containing the substrate can be moved, especially in a continuous processing method. It is preferred to form a plasma on the substrate because the substrate and the substrate The plasma-generating garment is displaced relative to the other over time. In a step (c) of a particular embodiment, the substrate is displaced relative to the plasma-generating device over time. relatively Preferably, the displacement of the plasma-generating device is at least 20 cm/min, preferably at least 50 cm/min, and most preferably at 8 cm/min, more preferably at most 3 cm/min. The coating may be deposited at a high deposition rate. In a preferred embodiment of the invention, a coating is preferably at least 0 〇 6 cm 2 · min at a rate of at least 〇〇〇 8 cin 2 .min. And even more preferably at least 22 mg / cm 2 · min. Compared to the use of air or a rare gas as a carrier gas or a balance gas, the method of the present invention can improve the power use efficiency to deposit a coating. Performing plasma polymerization to form a 20 optically clear coating on the substrate is preferred. The term "optically transparent" is used herein to describe a coating having an optical transparency of at least 70% to at least 9〇% is more preferred and at least 98% is preferred, turbidity is preferably not more than 1%, and more preferably not more than 2% and not more than 1%. The optical transparency is the ratio of the transmitted-non-scattered light to the sum of the transmission-scattering and the transmitted-scattered light (<25.) 21 200827469. The turbidity is the ratio of transmitted-scattered light (>2.5) to the total transmitted light. These values are measured according to ASTM D 1003-97. The process of the present invention can produce a unitary and substantially uniform coating at a high deposition rate and/or low power concentration compared to prior methods. *5 Embodiments The present invention is further illustrated by the following examples, which are not intended to limit the invention. All parts and percentages are by weight unless otherwise stated or used in the art. 10 Test Procedure 10 A polycarbonate substrate having a width of 10 cm and a thickness of 0.25 吋 (0.635 cm) was placed on a conveyor belt to pass a Gerneration 2 at a rate of 2 meters per minute. • 4 electrode APC 2000 atmospheric plasma coating | § (both from Sigma Technologies of Tucson, Arizona, LL 3.A.). The dimensions of the electrode are such that when the substrate is passed through a plasma paste, energy can be applied to a 54 cm2 region covering the full width of the substrate. The gas mixture used in the respective examples contained 250 standard milliliters per minute of sweeping TMDSO. Gas was introduced as a gas mixture component in Comparative Example 1 and Inventive Examples 1 to 4 to provide nitrogen gas and oxygen gas (as an oxidizing gas). The average linear gas volume of the gas 20 mixture in Comparative Example 1 and Examples 1 to 4 was 300 ft. / min. (91.4 m / min.). The average linear gas volume of the gas mixture of Comparative Example 2 was 80 ft./min. (24.4 m/min·). The introduced gas mixture is introduced over the substrate by a gas transfer tube having a drilled hole. When the gas mixture passes through the electrode and fills the space between the electrode and the substrate of the 200827469469, 2kw of electricity is applied to the electrode for a period of one minute while the substrate passes through the plasma coater. Thus, the 2 meter substrate of each example was subjected to plasma-enhanced chemotherapeutic gas deposition at a power concentration of 37 W/cm2. The film thickness measurement was measured using the Filmetrics F20 film thickness measuring device and the FILM MeasureTM software from Filmetrics, San Diego, Calif., and the results are summarized below.

Test data and results The data obtained by the above test procedure are shown in Table 1. Test results Example design AIR (SLPM) 氦 (SLPM) he/n2 Volume ratio VOL% HE Thickness (micro comparison example 1 84 0.25 0.004 0.3 __\ W person / _ 0.2 Comparative Example 2 0 15.25 NA 100 NM(1) 1 84 2.25 0.03 2.3 0.43 2 84 5.25 0.08 5.9 ^ 042 3 84 10.2 50.16 10.9 0.43 4 84 15.25 0.23 15.4 0.41 Rough and too powdery so The deposition thickness was not measured, so that it was not possible to add oxygen having a concentration ranging from 2.3 to 15.4 vol% as shown in the data of Table 15 as shown in Table 1, resulting in a coating having a thickness at least twice that of Comparative Example 1 (not carried out with ruthenium). Example 2 was carried out with hydrazine but without air, which provided an unsatisfactory powder coating as shown in the SEM image of Figure 1. The SEM image of Figure 2 shows that Comparative Example 1 provides Comparative Example 20 Example 2 is a smooth coating. However, comparing the SEM image of FIG. 2 with the image of SEM image 23 200827469 of FIG. 3, the coating obtained in Example 4 of the present invention is shown as the method of Example 4'. The coating produced was compared to Comparative Example 1 Making coatings it more smooth.

The method of the invention is used to manufacture a surface modification coating, such as an adhesive 5 accelerator or an anti-fog coating; an optical coating such as a reflective or anti-reflective coating; a spectral management coating coating, Or UV protective coating; chemical resistant coating: a wear resistant coating: or a gas barrier coating. Possible end use examples include 10 extruded plastic films, sheets for architectural glazing, glazing panels, solar collectors, appliances, optical consumables and devices, packaging, labeling and shipping moldings. The layer is coated on the line. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a reproduction of a scanning electron microscope (SEM) image showing the surface morphology of a polycarbonate substrate coated in Comparative Example 2 as described below. 15 Fig. 2 is a reproduction SEM image showing the surface morphology of the polycarbonate substrate coated in Comparative Example 1 as described below. Fig. 3 is a reproduction SEM image showing the surface morphology of the polycarbonate substrate coated in Example 5 as described below. [Main component symbol description] (none) 24

Claims (1)

200827469 X. Patent Application Range: 1. A method for coating or modifying a substrate comprising: (a) providing a substrate having at least one surface; (b) providing a gas mixture adjacent thereto (a) at least one surface of the substrate; (c) the gas mixture in (b) produces a plasma, and (d) the plasma in (c) forms a solid on at least one surface of the substrate Deposition, Wherein the gas mixture comprises: at least 35% by volume of nitrogen: at least 50 ppm of at least one gas precursor; optionally comprising an oxidizing gas for the gas precursor: and at least one rare volume ratio of at most 1.5:1 a gas and nitrogen gas, the rare gas comprising at least 1% by volume of helium, at least 1% by volume of helium or at least 3% by volume of argon, or a mixture thereof, each volume being at 20° of the gas mixture Total volume under C and 101 kPa pressure. 2. For the method of claim 1, the volume ratio of the rare gas to the nitrogen gas in the gas mixture of (b) at 20 ° C and 101 kPa is 1:1 or lower. 3. For the method of claim 1, the volume ratio of the rare gas to the nitrogen in the gas mixture of (h) at 20 ° C and 101 k P a is 1: 2 or lower. 4. The method of any one of claims 1 to 3, wherein the gas mixture of (b) 25 200827469 gas mixture comprises from 1 to 37 vol% (by the gas mixture at 20 ° C and Total volume under pressure of 101 kPa). 5. The method of any one of claims 1 to 4, wherein the gas mixture of item (b) comprises a range of from 2 to 10% by volume (at 20 ° C and 101 kPa of the gas mixture) Total volume under pressure). 6. The method of any one of claims 3 to 5, wherein the gas mixture of (b) comprises at least 45% by volume of nitrogen (based on the total volume of the gas mixture at 20 ° C and 101 kPa pressure) ). 7. The method of any one of clauses 1 to 7 wherein the gas mixture of item (b) optionally contains at least 5% by volume of the oxidizing gas (at 20 ° C and 101 kPa of the gas mixture) Total volume under pressure). 8. The method of claim 7, wherein the oxidizing gas comprises oxygen, nitrous oxide, ozone, nitrogen monoxide, and nitrous oxide, and combinations thereof. 9. The method of claim 7 or 8, wherein the gas mixture of (b) comprises at least 10% by volume of oxygen (based on the total volume of the gas mixture at 20 ° C and a pressure of 10 kPa). 10. The method of any one of claims 1 to 9, wherein the gas precursor comprises at least one cerium-containing compound represented by the following chemical formula (I): R3Si[X-Si(R,)2] rR" (I) wherein R, R' and R" each represent -Η, -OH, a C^o hydrocarbyl group, or a Cmo alkoxy group; X represents -Ο- or -N (R'''')_, where each occurrence of R'm represents -Η or a C^o hydrocarbyl group and r 26 200827469 represents 0 or a range from 1 to 10. 11. The method of claim 10, wherein the gas precursor comprises a decane or a decane compound. 12. The method of any one of claims 1 to 9, wherein the gas precursor comprises at least one metal-containing compound represented by the following chemical formula (1): MRaXb (II) wherein Μ represents Zn, Sn, A1 and a metal of Ti; R, each of which represents -H, -OH, a Cl_1G hydrocarbyl group or a Cl lQ alkoxy group; X represents a halogen, including C1 or Br; and "a" and "b The integers representing the 11 and :^ parts, respectively, are within the range of the valence of the M as previously described. Let the total number of a+b be equal to the valence of the metal ruthenium; or its volatile salt. 13. The method of claim 12, wherein the at least one metal-containing compound comprises diethyl zinc, dimethyl zinc, zinc acetate, titanium tetrachloride, tin dimethyl diacetate, zinc acetylacetonate, Hexafluoroacetamidine oxime, zinc carbamate, trimethylindium, triethylindium, (2,2,6,6-tetramethyl-3,5-heptanedionate) ruthenium (IV) and the like a mixture. The method of any one of claims 1 to 13, wherein the gas mixture pressure is 101.3 kPa + eight 20 kPa. The method of any one of claims 1 to 14, wherein the plasma is at a frequency of at least 2 kHz and not more than 100 kHz and b) by a dielectric shielding discharge device. Operation occurs at power concentrations from w/cni2 to 140 W/cm2. 16. The method of claim 15, wherein the power concentration range is from 27 W 2008/2008 to from 40 W/cm 2 to 40 W/cm 2 . 17. The method of claim 16, wherein the solid deposit is deposited on the substrate at a rate of at least 0.008 mg / (cm 2 · min). 18. The method of claim 16, wherein the solid deposit is deposited on the substrate at a rate of at least 0.06 mg / (cm 2 · min). The method of any one of claims 1 to 18, wherein the substrate comprises at least one polymer selected from the group consisting of polycarbonates, polyurethanes, Poly(meth)acrylate, polypropylene, polyethylene, ethylene/α-anthracene copolymer, styrene-acrylonitrile copolymer, polyethylene terephthalate and polybutylene terephthalate ester. 20. A coated substrate obtainable by the method of any one of claims 1 to 19. 28 200827469 , VII. Designation of representative representatives: (1) The representative representative of the case is: (3). (2) A brief description of the symbol of the representative figure: (none) 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: