Plasma coloring and pigment fixing method and system

Abstract

A system for coating an article includes a pigment applicator configured to apply a pigment and a plasma module. The plasma module is configured to generate a plasma region. At least one of a chemical agent and a precursor may be used to supply a plasma generated in the plasma region such that the plasma region may at least partially polymerize the at least one of the chemical agent and the precursor to form a plasma polymerized coating. The pigment may be secured to the article by a plasma polymeric coating.

Description

Technical Field

[0001] The present disclosure relates to changing the visual appearance of a substrate by applying a coating treatment to the substrate. In particular, the present disclosure relates to using a plasma process to apply dyes or pigments and fix them on the surface of the substrate. Background Art

[0002] Traditional dyeing methods are well-known in the field of textile manufacturing. However, these conventional methods usually have problems of resource waste and are difficult to meet the sustainable development requirements of textile dyeing and dyeing or coloring of other articles.

[0003] Such processes typically require a large amount of water resources, chemical agents, and a considerable amount of energy and / or fossil fuels to obtain the finished product. In addition, the dyeing process in textile preparation can be one of the following multiple steps, which requires the textile fabric to be dried through a stenter or other system. In addition, based on textile dyeing or coloring processes, natural fibers and synthetic fibers or different textile components often require specific treatment methods, resulting in a significant increase in the processing complexity of different materials.

[0004] In view of the major challenges faced by traditional dyeing systems and methods, there is an urgent need to adopt more efficient and / or environmentally conscious alternative solutions to replace existing methods and systems to alleviate one or more problems.

[0005] Textile materials generally include the following materials, such as fibers, yarns, fabrics, and textile derivatives. Textile colorants in traditional processes are provided in a liquid form, usually a solvent for dissolving dyes, or a solution and dispersion containing pigments or powders.

[0006] Textile colorants are used to dye textiles. The colorant is usually the color presented by the textile, but the color of the textile may be enhanced or changed due to the opacity or other properties of the dye or pigment. Although it is desirable for the colorant to be permanently bonded to the textile, the bonding strength is often less than expected.

[0007] Some colorants can form chemical bonds with textiles, some are physically trapped in textile fibers, and the rest require additional fixing agents to achieve the bonding of the colorant to the textile. Dyes and pigments are commonly used for textile coloring, where dyes usually exist in solution form, while pigments are mostly insoluble.

[0008] Dyes are usually used to penetrate the fibers and impart color from the inside. In contrast, pigments usually cannot penetrate the fibers but are deposited around the fibers and require adhesives or other adhesion means to fix the pigments. Due to these essential differences in the coloring mechanisms, the methods of applying and coloring textiles are also very different.

[0009] Dyes are generally water-soluble and may have a binding affinity for specific textiles. Adsorption typically occurs between textile fibers and dyes due to the chemical interaction between the textile fibers and the dye chemicals. Some dyes can be reactive dyes and attach to chromogenic molecules, whereby a portion of the dye reacts with the textile fibers, causing the chromogenic molecules to attach to the fibers in the desired color. Such chemical reactions can form different chemical bonds with varying bond strengths.

[0010] Pigments generally have no attraction to textile fibers and rely on auxiliary components or binders to adhere to the fibers. Pigments can be dissolved or suspended in a solution and are dissolved or suspended based on the carrier medium.

[0011] In other cases, when using pigment or dye colorants, the colorants need to be applied to the textiles to be treated through at least one wet processing step. Wet processing equipment and drying equipment are generally large in volume and high in equipment cost, and at the same time, they can cause various textile processing complexities. These complexities involve fabric setting, shrinkage rate, hardness, drape, and post-finishing handfeel. To address these complexity issues during the drying process or simply due to the coloring process itself, additional chemicals may need to be added during the wet processing stage. In addition, these additional chemicals may cause visible powder marks or other defects, and further processing steps are required to solve this problem before the textiles can meet the finished product requirements.

[0012] Traditional dyeing processes generally consume a large amount of water resources and often produce a large amount of waste chemicals, such as dyes entering the environment. Dyes can significantly damage the sensory quality of water bodies, increase the biochemical oxygen demand (BOD) and chemical oxygen demand (COD), interfere with photosynthesis, inhibit plant growth, have a bioaccumulation effect through the food chain, and may be toxic, mutagenic, and carcinogenic. Therefore, reducing wastewater discharge has significant advantages.

[0013] In view of the defects and limitations of traditional dyeing methods, it is necessary to improve, adjust, or replace the existing methods with more environmentally conscious methods and systems for implementing such methods.

[0014] Any discussion of the prior art in this specification should not be construed as an admission that such prior art is common general knowledge or forms part of the general technical knowledge in the field. Summary of the Invention

[0015] Problems to be Solved

[0016] It is advantageous to provide a system and / or method suitable for dyeing natural and synthetic materials.

[0017] It is advantageous to provide a system that can dye or color a substrate and reduce water consumption.

[0018] It is advantageous to provide a system that can reduce carbon emissions compared to traditional dyeing and finishing processes.

[0019] It is advantageous to provide a system that can complete the dyeing and finishing processes in a single roll-to-roll process.

[0020] It is advantageous to provide a dyeing method that can achieve single-sided dyeing of a substrate.

[0021] It is advantageous to provide a new dyeing method that consumes fewer resources.

[0022] It is advantageous to provide a dyeing method for dry dyeing.

[0023] It is advantageous to provide a fixing and / or binding process that can fix or capture particles, pigments, and / or powders on the surface of an article.

[0024] It is advantageous to provide a method that can more efficiently achieve substrate dyeing.

[0025] It is advantageous to provide a method and process that can bind particulate matter to the surface of an article.

[0026] The present invention aims to overcome or improve at least one defect of the prior art, or provide a beneficial alternative.

[0027] The method for solving this problem

[0028] In a first aspect, there is provided an article coating system. The system may include: a pigment applicator adapted to apply a pigment; a plasma module adapted to generate a plasma region; supplying at least one of a chemical agent and / or a precursor to the plasma region, and at least partially polymerizing at least one of the chemical agent and / or the precursor in the plasma region to form a plasma polymerized coating; wherein the pigment is fixed to the article through the plasma polymerized coating.

[0029] Preferably, the system further includes a post-plasma treatment module adapted to process the plasma polymerized coating. Preferably, the pigment applicator can be integrated with the plasma module. Preferably, the plasma module can be housed in a chamber that is locally purified of plasma gas to a purity exceeding 90%. Preferably, the chamber inlet can be configured with an inlet sealing roller such that while allowing the article to enter the chamber, the plasma gas is substantially maintained in the chamber and external fluid entry is restricted. Preferably, the pigment applied to the article can be at least one of a colorant, a functional pigment, and a conductive pigment. Preferably, the plasma module is adapted to supply at least one of a chemical agent and / or a precursor to the plasma region, such that at least one of the chemical agent and / or the precursor forms plasma polymerized molecules before being applied to the article to form a plasma polymerized coating.

[0030] On the other hand, there is provided an article having a plasma coating. The article includes a surface on which a pigment is deposited. The pigment is bonded to the article through a plasma polymerization coating, wherein the polymerization pressure of the plasma polymerization coating is between 95 kPa and 105 kPa.

[0031] Preferably, an additional pigment deposition layer may be applied on the surface of the plasma polymerization coating. Preferably, the additional pigment deposition layer may be fixed to the plasma polymerization coating through an additional plasma polymerization coating. Preferably, a pigment may be provided to the article during the plasma polymerization step such that the pigment is incorporated inside the plasma polymerization coating during coating. Preferably, the pigment particle size may be relatively larger than the coating thickness. Preferably, the pigment may be a colorant different from the color of the article, so that the whole article presents the chromaticity and similar color of the pigment colorant. Preferably, the pigment may be a functional pigment that can release and / or diffuse ions when incorporated in the plasma polymerization coating. Preferably, the plasma polymerization coating is completed through a post-plasma treatment step to cure or treat the exposed surface of the plasma polymerization coating.

[0032] In the context of the present invention, terms such as "comprising", "including" should be construed in a broad sense, that is, "including but not limited to", rather than an exclusive meaning.

[0033] The interpretation of the present invention should be based on at least one technical problem described or related in the background art. The present invention aims to solve or improve at least one technical problem, and thereby one or more beneficial effects as defined in the present specification and elaborated with reference to the preferred embodiments can be achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 Shown is a schematic diagram of a system including one or more processing modules for article processing.

[0035] Figure 2A Shown is a side view of a schematic diagram of a system including a plurality of article processing chambers.

[0036] Figure 2B Shown is a side view of another system for applying a colorant to an article.

[0037] Figure 3 Shown is a side view of another embodiment that can be used to apply a colorant to an article.

[0038] Figure 4 Shown is a side view of an embodiment of a module and a dispensing system.

[0039] Figure 5A Shown is a side view of an embodiment of a plasma region generation module.

[0040] Figure 5B Shown isFigure 5A Another side view, which shows multiple different plasma regions or fluid distribution states. Detailed implementation mode

[0041] The preferred implementation mode of the present invention will be described below in conjunction with the accompanying drawings and non-limiting embodiments.

[0042] Reference numerals

[0043] 1 Article

[0044] 10 System

[0045] 11 Terminal

[0046] 12 Frame

[0047] 15 (15A - 15C) Chambers

[0048] 18 Pigment applicator

[0049] 20 Module

[0050] 21 Post - treatment module

[0051] 22 Housing

[0052] 30 Power supply

[0053] 40 Fluid delivery system

[0054] 45 Cooling system

[0055] 50 Mixing chamber

[0056] 55 Atomizer

[0057] 60 Roller

[0058] 70 Recirculation system

[0059] 80 Support mechanism

[0060] 85 Pumping system

[0061] 90 Exhaust system

[0062] 95 Storage device

[0063] 100 Electrode

[0064] 102 Core

[0065] 104 Sheath

[0066] 106 Channel

[0067] 108 Fluid channel

[0068] 110 Reaction gap

[0069] 112 Plasma region

[0070] 114 Gas conduit

[0071] 116 Through-hole

[0072] 118 Bias source

[0073] 120 Bias voltage

[0074] 130 Carrier fluid supply device

[0075] 140 Monomer supply device

[0076] 150 Pigment supply device.

[0077] The system described herein is for materials processing, and the materials may include substrates, sheet materials, three-dimensional objects, and irregular objects, collectively referred to as "article 1". The system 10 is suitable for the processing of any desired article 1, and several embodiments may specifically refer to substrates or other planar articles. Similarly, this does not constitute a limitation that the system can only be used for the processing of substrate 1.

[0078] The system 10 shown in the embodiments of the respective figures includes several plasma processing modules 20 for processing the substrate 1. The system is preferably suitable for a plasma enhanced chemical vapor deposition (PECVD) process, in which chemical agents, monomers, or precursors are polymerized by plasma to form a plasma polymerized coating or film. The processing module 20 can be a showerhead module, a spraying module, a deposition module, a plasma module, or any other module that can achieve surface activation or coating, and can apply dry and / or wet coatings that need to be cured. If a dispersion is applied, it is advisable to evaporate or remove the dispersion fluid before entering the processing module 20. Each module 20 is detachably installed in the system 10 for pre-processing, post-processing, processing, coating, covering, depositing, activating, or other required processes on the article 1. Preferably, the processing implemented by the processing module 20 includes depositing pigments and / or microparticles on the article 1 through a plasma via a nozzle, but the pigment applicator 18 can also be an independent unit or module that can apply pigments before the processing of the module 20.

[0079] The article 1 can be conveyed under the processing head 20 by a conveying device. Any suitable conveying device can be used, such as a conveyor belt, a moving platform, a roller, or other predetermined devices. Figure 1 And in the embodiment of the system 10 shown in FIG. 2, a roller is used to convey the substrate article 1 through the chamber 15.

[0080] In another embodiment, the article 1 can be placed directly below the processing module 20, and the article 1 can be processed without being transferred from a first position to a second processing position. This configuration is particularly useful if a single article 1, rather than continuous articles on a production line, needs to be coated or processed. Thus, the system 10 can serve as a sterilization device, a surface activation device, or a selective processing system.

[0081] The processing module 20 can implement at least one of physical modification, chemical modification, coating, film application, surface activation, sterilization, polymerization, or other desired processing techniques. The system 10 can include any number of modules 20 to perform the processing.

[0082] It should be understood that in some embodiments, when using a gas delivery tube or a pressurized plasma fluid, the pressure in the chamber 15 can be higher than atmospheric pressure. The pressure range can be from 10 Pa to 1 MPa. In some embodiments, the pressure range can be from 95 kPa to 110 kPa, with the ambient pressure being approximately 101 kPa. In other words, the pressure can be the ambient pressure or ±5 kPa of 1 atmosphere. Different from traditional systems, this pressure can be increased above atmospheric pressure instead of tending towards vacuum decompression. Similarly, the system 10 can be adapted to operate at or above atmospheric pressure, which is particularly advantageous. Optionally, the pressure in the chamber 15 can have a negative pressure to assist in exhausting the gas and other fluids in the chamber 15. The negative pressure range of the chamber 15 is 90 - 100 kPa, or ±10 kPa of atmospheric pressure, and in a more specific embodiment, it is ±1 kPa of atmospheric pressure.

[0083] Traditional plasma processing devices typically need to process articles in a vacuum or low-pressure chamber. Plasma is generally not used outside a closed decompression chamber because using plasma in a non-vacuum chamber causes many problems. Although a vacuum system is more likely to generate and maintain plasma, the present system 10 can solve this technical problem by establishing a high-purity or fluid-controlled chamber under near-atmospheric pressure conditions. Although introducing gas into the chamber 15 is relatively simple, it is more difficult to provide chemical agents for polymerization while maintaining internal purity, or to polymerize chemical agents, monomers, or precursors on the article. Therefore, the system 10 can be configured with a series of interlocks or air locks to reduce fluid infiltration and / or exfiltration into and out of the chamber 15 when transporting the article 1. In addition, one or more evacuation positions and a recirculation system 70 can be used to purify the fluid and return it to the system 10.

[0084] Vacuum systems also have problems with uneven distribution of carrier fluids and the monomers contained therein. Another technical difficulty is that when introducing fluids into the plasma region or reaction gap, it may cause polymerization or molecular ionization of dangerous / undesired molecules, thereby damaging the substrate 1 to be processed or affecting the processing quality. The system modules 20 described herein can effectively solve these problems.

[0085] In addition to the above problems, another significant drawback of the existing system is that it must operate under a vacuum state. Not only does it take a large amount of time to achieve the vacuum degree, but injecting the aerosol usually causes the overall pressure in the vacuum chamber to increase, resulting in system failure. The aerosol injected into the vacuum environment will also diffuse and cannot be effectively utilized. Therefore, the system and method described in this disclosure are advantageous compared to the prior art.

[0086] Another significant advantage of the present system 10 is that an aerosol can be used to transport monomers and / or pigments to the plasma region for coating methods. The aerosol can be used to carry pigments, salts, organic particles or inorganic particles to the plasma region or other target locations within the chamber 15. As previously mentioned, an atomizer can be used to convert at least one fluid into a vapor or aerosol. This vapor can be regarded as in the form of an "atomized stream", which can contain one or more monomers and / or one or more pigments. Optionally, the pigment or other particles can be dispersed in the atomized stream formed by the atomizer or vaporizer.

[0087] The aerosol can be transported to the chamber 15 through the fluid outlet and introduced into the plasma region directly or by gravity. The aerosol can be directed to the plasma region, where at least 50% of the aerosol passes through the plasma region and is then deposited on the target area of the article 1. A coating of 50 nanometers per minute - 400 nanometers per minute can be achieved by this method. In another embodiment, the coating can reach 100 - 300 nanometers. In another embodiment, the coating deposition rate is about 150 nanometers per minute. If the pigment is applied alone, the pigment deposition can be independent of the coating thickness; however, before the formation of the plasma polymerization coating, the pigment can also have a specific deposition rate. The pigment loading rate ranges from 0.25 grams per minute per meter width - 360 grams per minute per meter width, depending on the particle size of the pigment applied. In some embodiments, the pigment transported to the article 1 is about 1.5 ± 0.5 grams per square meter, or generally 0.5 grams per square meter - 5 grams per square meter. The coating thickness can be the thickness of the plasma polymerization coating without pigment, or can additionally include the thickness of the previously deposited pigment layer. For example, if a 400 - nanometer - thick pigment - loaded layer or layer is applied and then a 100 - nanometer plasma polymerization coating is applied, the total coating thickness will be in the range of 400 - 500 nanometers thick, depending on the total pigment coverage and the ability of the plasma polymerization coating to fill the pigment gaps to form a final plasma polymerization coating with the pigment embedded or fixed therein.

[0088] In contrast, systems that employ vacuum pressure cannot achieve a similar coating effect because introducing an aerosol into a vacuum or near-vacuum environment causes the pressure to rise and immediately results in the aerosol diffusing within the vacuum chamber rather than being transported to the target area or the plasma region 112. Even when a plasma region 112 is provided at the aerosol outlet, numerous plasma irregularities still occur during aerosol injection, and the particles will diffuse within the chamber and not flow in a predetermined direction. Traditional systems that use vacuum or low pressure also have other known drawbacks.

[0089] In another embodiment, pigments can be mixed into the aerosol. In this way, powders or particles of a specific particle size can be transported through the fluid system to the plasma region 112.

[0090] In another embodiment, a separate stream of pigments or clusters can be provided and directed to the plasma region after being mixed with the outlet fluid. Optionally, the pigments can be applied to the surface of the article 1 by spraying, scraping, wiping, or jetting.

[0091] Referring to Figure 1 , the illustrated system 10 can be used to process an article 1. The article 1 can be a substrate, typically in a planar or two-dimensional form, and can be processed by a roll-to-roll process. The illustrated article can be a linear substrate, porous, non-porous material, fabric / non-fabric, knitted or other textile, or film. Other embodiments of the system can apply surface coatings to three-dimensional articles, and the articles can pass through the system by means of a conveyor belt, fixture, clip, or other fixing mechanism. Alternatively, the three-dimensional article can be processed in a fixed position, and the system processing head can move towards or away from the article 1 to process the article.

[0092] For example, a single chamber 15 can be provided to first apply a pigment or particle coating to the article 1, and then the pigment applicator 18 can be moved away or deactivated, and the plasma processing device 20 can be moved to its position and / or activated to perform plasma coating and / or plasma processing. Optionally, the same processing module 20 can be configured to simultaneously supply dissolved or carrier-fluid-state dyes and / or pigments to the article 1 and perform plasma processing and / or plasma coating on the article 1. The carrier fluid can be an aerosol, vapor, liquid, gas, etc. More than one monomer supply source can be configured, and fluids can be selectively introduced from these supply sources as needed.

[0093] In another embodiment, the system 10 may be configured with a chamber 15 of a pigment applicator 18, which is capable of applying pigments to the article. One or more pigment applicators may be provided, and each applicator 18 may be configured to apply the same or multiple pigments, which may be a single pigment or colorant. After applying the pigments to the article, the system 10 transports the article 1 to a region adjacent to the plasma module 20, and the plasma module provides a plasma-formed polymer film or polymer coating to the article 1. During the plasma polymerization process, the article 1 may be adapted to continuously move under the module 20, thereby providing a continuous coating to the article 1. When the article 1 moves under the module 20 and receives the plasma coating or has a coating polymerized on the article 1, the article 1 may enter the processing area of the post-treatment module. The post-treatment module may be used to cure, finish, gloss, provide a matte effect, or provide texturing to the plasma polymerization coating on the article.

[0094] It should be understood that in this embodiment, the system 10 may synchronously provide chemical agents, monomers, or precursors to the article during pigment application and / or polymerization. If both the pigment applicator 18 and the module 20 are capable of providing chemical agents, monomers, or precursors, they may be the same or different chemical agents, monomers, or precursors. Additionally, regardless of the device for applying the chemical agent, monomer, or precursor, the plasma module 20 is preferably adapted to polymerize or substantially polymerize the chemical agent, monomer, or precursor on the article. The degree of polymerization may also depend on the end use of the article, and the plasma module 20 may be configured to only partially polymerize the chemical agent, monomer, or precursor that forms the coating of the article 1. This feature is particularly applicable to pigments that require the releaseability of the article to be retained, such as drug sustained release. The partially polymerized plasma polymerization coating may also be suitable for other uses or applications.

[0095] A user terminal 11 communicable with the system 10 may be provided for inputting parameters, selecting fluids, monitoring the chamber status, and starting and stopping a process. Any suitable terminal interface may be employed, and the terminal may control the movement of one or more components in the system 10. Software may be executed through the terminal and remotely updated. Preferably, the storage medium in the terminal 11 may be used to store processing data and store data related to system errors, unauthorized use, or access.

[0096] See Figure 2A, the system 10 is provided with a first processing chamber 15A, a second processing chamber 15B, and a third chamber 15C. It should be understood that all the chambers 15 can be integrated into a single chamber 15, or two or more chambers as shown in the figure can also be adopted. The first chamber 15A can be a pigment application chamber 15A. Optionally, a plurality of pigment application chambers can be provided, and respective pigment applicators 18 are configured to apply a predetermined pigment or colorant to the article 1. The discrete pigment application chambers can reduce the risk of pigment cross-contamination. If the pigment application chamber includes a spraying device that can spray a dispersion or other liquid onto the article 1, the system can be provided with another chamber (not shown), which includes a drying section. Alternatively, the drying section can be located within the spray application chamber 15A and includes at least one heater or device for removing the liquid before the article contacts the plasma region. The second chamber 15B can be a plasma processing chamber 15B, and the third chamber can be a post-processing chamber 15C configured with a post-processing module 21. The post-processing module 21 can include at least one of the following devices: a heating device, a cooling device, an additional module 20, a plasma device, or a shaping device, for applying an additional coating, completing a polymerization process, or modifying the plasma coating applied by the module 20. The chamber 15 is preferably sealable to form a fluid seal that can maintain the required local atmosphere. Optionally, the chamber can be provided with an inlet and an outlet, so that the flat article 1 can enter the chamber 15 for processing and leave the chamber after processing. The inlet and outlet are preferably provided with seals to prevent or substantially reduce the infiltration of gases outside the chamber 15. The roller 60 can be used to convey the article through the chamber 15.

[0097] Each chamber 15 can be adapted to a specific part of the process, and each chamber 15 can have at least one of independent pressure, atmosphere environment, processing module, and length. The first chamber 15A can apply a pigment to the article 1 through the pigment applicator 18, and the pigment can be applied in the form of dry powder particles or carried or dispersed in a liquid. When applied in a dry substance, the pigment can be sprayed onto the article so that the article substantially captures the pigment on its surface, or a velocity is provided to the pigment so that it at least partially penetrates into the article 1. When it is necessary to dye textiles with a colorant, the penetration characteristics of the pigment have special application value.

[0098] An interlock device or an air lock can be provided between the first chamber 15A and the second chamber 15B (similarly, the third chamber 15C can also be configured with an interlock device or an air lock) to maintain the predetermined operating conditions of each chamber and substantially prevent uncontrollable pollutants from entering. Each chamber in the system can be configured with an air lock, a roller, or a fluid control device at its respective inlet and outlet. An air lock is preferably used to maintain the required atmosphere in the chamber, ensure the desired processing, and prevent unknown pollutants from entering the processing process.

[0099] In another embodiment, the system does not include an air lock between the chambers. In this case, the chamber 15B can be configured to have a relatively higher pressure than other chambers, so that the gas supplied to the chamber 15B is pressed towards other chambers of the system.

[0100] In another embodiment, a high-pressure section may be provided between the chambers to supply plasma gas or other required gases to the chambers. This configuration can cause the fluid to be pressed from the high-pressure section into the adjacent chamber.

[0101] In another embodiment, the system 10 may be configured with a pretreatment chamber located in front of the pigment application chamber 15A, which is similar to the chamber 15C but functions as a pretreatment chamber rather than a post-treatment chamber. This pretreatment chamber may be adapted to apply a primer to the article 1 to receive the pigment thereon. The pretreatment chamber may alternatively be used to activate or modify the surface of the article before pigment application. The primer may be a coating formed by at least partially polymerized hexamethyldisiloxane (HMDSO), argon plasma treatment, nitrogen plasma treatment, or oxygen plasma treatment. It should be noted that any of the above reaction gases can be mixed with argon or other inert gases in any proportion. The reactive particles can be temporarily bonded to the surface of the article, enhancing the adhesion in the subsequent pigment application step. Optionally, mixing two reactive gases is advantageous.

[0102] The temperature of the chamber 15 can be regulated by injecting gas therein, and the average temperature inside the chamber can be maintained in the range of 15 °C to 35 °C. Within this range, the deposition rate of the article to be processed is significantly better than that outside this range.

[0103] The temperature of the plasma fluid and / or monomer when entering the chamber can be in the range of 10 °C to 50 °C. The excitation in the plasma region will increase the temperature of these fluids, resulting in an increase in the temperature of the chamber 15. Certain chemical agents, monomers, and precursors may require a temperature of up to about 250 °C during vaporization or atomization, and at this time the chamber temperature may exceed the above range, but this is also a feasible embodiment of the system, and the chamber can be adapted to handle the working conditions in this temperature range. In other words, as needed, the temperature of the vaporized, evaporated, or atomized fluid injected into the plasma region can be directly used as the internal temperature of the chamber.

[0104] In another embodiment, at least one consumable of the system, such as carrier gas, monomer, plasma gas, pigment, or the solution used with the system, can be temperature-controlled separately. The temperature of each consumable can be controlled in the range of -10 °C to +150 °C. Other temperature ranges are also applicable, as long as they are between the freezing point of the consumable and the evaporation temperature when the consumable enters the fluid supply line or the plasma region. It is advantageous to increase the temperature of certain consumables because this can increase the probability of cracking when entering the plasma region, thereby forming a more durable or specific-performance coating. In addition, by increasing the temperature of the corresponding monomer or pigment, the carrier gas can carry a greater volume of at least one of the monomer and / or pigment. Alternatively, the temperature of the carrier gas can also be increased to increase the carrier gas to carry additional monomer and / or pigment.

[0105] In the fluid delivery system 40, a photoionization (PID) sensor, a fluid flow sensor, a temperature sensor, or other fluid sensors can be employed to monitor and control fluid dispensing. The sensors can also determine the concentration and fluid extracted from the chamber for recirculation in the recirculation system 70, as described hereinafter. Based on the detected concentration and composition of the fluid extracted from chamber 15 and injected into the recirculation system 70, the initial fluid concentration and volume of the fluid supply can be varied to form a more uniform mixture. It should be noted that the recirculated fluid and the initial fluid can jointly form the desired concentration for supplying chamber 15. The desired concentration to be supplied can be used to form a plasma region and / or apply a polymeric coating to the article 1.

[0106] In another embodiment, the recirculation system is provided with a storage device 95, which can be a storage tank or other container. More than one storage device 95 can be configured to store the separated fluids. For example, the first storage device stores the carrier fluid, and the second storage device stores the monomer or partially polymerized monomer. The storage device 95 can temporarily store the collected fluid and can be returned to the recirculation system 70 or removed for further processing and purification.

[0107] An atomizer 55 can be used to atomize the monomer and the pigment, and transmit them through the fluid delivery system to the reaction gap 110. The atomizer 55 can be disposed within the mixing chamber 50. In this embodiment, the module 20 with the reaction gap 110 functions as both a pigment applicator and a plasma polymerization coating device.

[0108] The mixing chamber 50 can be used to mix the pigment and the monomer in a predetermined volume to obtain the desired monomer-pigment ratio. A syringe or metering device can be used to inject a predetermined volume of monomer fluid and / or pigment fluid to be mixed into the mixing chamber 50, followed by atomization. The mixing chamber forms part of the fluid delivery system 40.

[0109] The fluid delivery system 40 can also include a plurality of gas conduits or pipes 114 for delivering fluid to the chamber 15. The gas conduits 114 include a plurality of gas outlets 116 for distributing pressurized gas into the chamber 15. The gas outlets 116 can deliver pure substances, such as the required fluid, to the chamber 15. The required fluid can include at least one of a monomer, a precursor, a chemical agent, a plasma gas, a liquid, a reaction gas, a Penning ionization gas, and a sacrificial gas. The gas outlets can also deliver at least one of a carrier fluid, a monomer, a monomer-pigment mixture, or a pigment-monomer mixture to the chamber 15. The polymerizable monomer and the pigment contained therein can be fixed within, on, or under the coating formed on the article 1.

[0110] The gas outlet 116 can eject a fluid such that a jet is formed when the fluid passes through the plasma and is directed towards the article 1. Thus, an unconventional plasma jet is formed because the plasma gas is ejected into the chamber atmosphere before being excited at the electrode 100 to form a plasma. It should be noted that the above-mentioned plasma jet is similar in appearance to the plasma torches known in the prior art, but the difference is that the jet is formed above the excitation zone and constitutes a low-temperature plasma flow. The advantage is that the jet can be formed by the fluid delivery pressure and is suitable for flowing through the free area above the electrode before entering the plasma region 112. This design enables the current-carrying fluid to also enter the area above the electrode, which helps to smooth the plasma generated between the electrodes 100 or form more uniform plasma that can extend to multiple sets of electrodes within the chamber 15.

[0111] The bias plate 120 can be used to attract ionized substances, thereby increasing the deposition rate or imparting ion fluid movement. The bias plate is preferably disposed below the module 20 so that the particles from the module 20 can be adsorbed onto the article 1. The bias plate 120 can be powered by a bias source 118 or by the power supply 30.

[0112] Preferably, the bias plate 120 is a negatively charged DC bias plate. Optionally, the DC bias can be replaced with an AC bias. It should be noted that the bias plate 120 can also be positively charged as needed. A Penning trap can be provided above and / or below the plasma region to repel or attract the ionized substances in the plasma region in a specific direction. Preferably, if a Penning trap is used and there is a bias plate, the polarity of the Penning trap is opposite to that of the bias plate. Magnetic fields can also be used to induce ion movement within the plasma region, causing positive ions and / or negative ions to move along a predetermined vector or direction. In another embodiment, the bias plate 120 can be configured as a DC bias plate or an AC bias plate that functions similar to an electrode, such that the module electrodes have a unified polarity and are opposite to the polarity of the bias plate.

[0113] Referring to Figure 5A and Figure 5B , an embodiment of the processing module 20 is shown. The module 20 includes a housing 22, which houses a plurality of electrodes 100 and at least one gas outlet 116. The housing 22 is used to support the electrodes 100 and the gas outlet 116 of the fluid delivery system 40.

[0114] The outlet 116 can be disposed within a diffusion plate (not shown) to assist in distributing the current-carrying fluid and the particles or fluids carried thereby. Figure 5A and 5BIn the illustrated embodiment, the gas conduit 114 is integrally provided with the gas outlet 116. And the gas conduit is located above the electrode 100. In a preferred embodiment, the gas outlet 116 is provided directly above the reaction gap 110 between the electrodes 100. Thus, the gas outlet can focus the delivery of gas to the reaction gap 110. The number of gas outlets can be equal to, less than, or at most two more than the number of reaction gaps 110. It should be noted, however, that the number of gas conduits within the module can be any number to deliver sufficient fluid to the electrode 100 and / or the chamber 15.

[0115] The article 1 is shown as being located below the opposing module 20 and configured to pass beneath the module 20. Passing beneath the module 20 allows for post-treatment of the coating on the article 1. The first module 20 within the chamber is optionally adapted to modify the functional groups remaining on the article after the application of the modified pigment. The functional groups can be modified by any suitable plasma gas, preferably an inert gas. Modifying the functional groups is advantageous because some of the dispersants used to apply the pigment may be hydrophilic, while the target coating may include a durable waterproof coating. Modifying the remaining functional groups can eliminate their functional properties, enabling the subsequent plasma coating to be more effectively applied to the article. Additionally, this modification can reduce the risk that the underlying remaining functional groups will undermine the intended function of the plasma coating. For example, modifying a hydrophilic coating to a neutral or non-hydrophilic coating can enhance the performance of a subsequent hydrophobic coating.

[0116] A roller 60 or a support mechanism 80 can be used to carry or transfer the article from the first side to the second side of the module, and the article 1' is the processed article. As shown in the figure, when the electrode 100 is energized to maintain the plasma in the reaction gap, the plasma region 112 can extend across multiple electrodes 100. It should be noted that the reaction gap is the initial formation region of the plasma, and this plasma region can initiate or excite the local atmosphere around the electrode 100 to generate plasma glow. Preferably, the plasma glow between multiple groups of electrodes 100 is substantially uniform, so that the area to be processed or coated is much larger than the area that can be reached by a plasma torch or a plasma jet in the same time. In addition, the plasma region formed by the electrodes is preferably located above the article 1 to be coated, so that the plasma does not need to directly contact the article 1, unless specifically required. Fluids, such as a carrier fluid, an atomized monomer, a monomer vapor, a monomer aerosol, and / or a pigment, can enter the chamber 15 from the outlet 116. These fluids can diffuse outward from the orifice 124, or be supplied under sufficient pressure to form a fluid column 126. The diffused fluid 124 can be used to distribute the fluid on the electrode 100 and form different fluid density regions. This helps to form a plasma region 112 that extends across multiple electrodes 100. Alternatively, the fluid column can be excited and form a plasma jet. This plasma jet can be used to form a dot coating or a more focused coating in some embodiments. Different from the traditional plasma jet, the plasma jet is a non-thermal plasma, and its fluid has been ejected into the open chamber 15 before reaching the electrode 100 to initiate or excite the plasma fluid. Therefore, the fluid injected into the chamber 15 can be mixed with the local fluid in the chamber 15 before reaching the electrode. This plasma formation method can also entrain or collect other gases in the chamber 15 that are not ejected from the outlet 114 and transport them to the reaction gap 110.

[0117] Optionally, the size of the outlet 116 can be changed by inserting a nozzle or other fluid direction or throttling device. The outlet 116 can be adapted to a threaded or mounting device to connect the nozzle, thereby changing the type or distribution of the fluid flow entering the chamber 15. The nozzle can also be used to direct the fluid to flow in a desired direction. If necessary, the nozzle can also be configured with a solenoid valve, an iris, or a closing mechanism to achieve sealing. This is particularly useful when multiple coatings or treatments are performed in the chamber 15, since the outlet can be selectively opened or closed.

[0118] Figure 4Shown is a side view of an embodiment of module 20, which includes a pigment applicator. The pigment applicator can be disposed below a manifold that delivers at least one of a plasma fluid and a chemical agent, monomer, precursor to a product. In another embodiment, the pigment applicator 18 can be located relatively above the manifold of module 20. The pigment applicator can be composed of a plurality of tubular sections for delivering a liquid and / or pigment to a reaction gap 110 in a plasma region before being applied to the product. A fluid reservoir can be provided to store fluid for the pigment applicator, and the pigment applicator can have a predetermined metering or control mechanism to introduce a desired amount of pigment into the plasma region.

[0119] The pigment applicator, which is part of module 20, has several advantages, particularly the Penning ionization effect that may occur when introducing the pigment into the plasma region. Additionally, the pigment and / or its carrier can polymerize in the plasma as a precursor. This is also advantageous for plasma polymerized dyes, which can apply a desired colorant and fix the dye to the product by mixing one or two chemical agents and subsequent plasma polymerization.

[0120] In other embodiments, as Figure 2A shown, the pigment applicator can be separated from the plasma module and is adapted to apply a dispersion to product 1. This can be advantageous because the dispersion liquid can be removed before the plasma region is generated in module 20.

[0121] The dispersion preferably has a high pigment concentration, where the pigment accounts for at least 30% by weight of the dispersion. More preferably, the pigment accounts for 60% to 90% by weight of the dispersion. In another embodiment, the pigment can be applied to the fabric in a "dry" form without a dispersant. The system can be configured to dilute the high-concentration dispersion as needed. In this configuration, a dose or quantity of the dispersion is mixed or combined with a fluid that dilutes the high-concentration dispersion. This configuration has particular advantages for different products 1 to be processed in the system. For example, if product 1 is a cotton substrate, the dispersion can be diluted at a first dilution ratio, and if product 1 is a polyester substrate, the dispersion can be diluted at a second dilution ratio. Each dilution ratio depends on the composition of the product, particularly in the case of textiles and other substrates. Although cotton and polyester are specifically listed, each substrate type can have a unique dilution ratio, or the same or similar dilution ratios can be used to apply the pigment to the substrate.

[0122] For a dispersion with a high pigment weight concentration, the dispersion can be closer to a paste and can be diluted as needed. A solvent or water can be used in system 10 to dilute the paste, and the diluted paste can then be applied to product 1 through a spray system.

[0123] Dispersants can be used to dilute pigment dispersions or provide the desired dispersion properties. In at least one embodiment, the following dispersants can be combined with pigments to form the fluid delivered to article 1: Tego Dispers 755W (10 - 200% of the pigment weight), Surfadol XL167 dispersant (10 - 50% of the pigment weight), Disperbyk-199 dispersant (20 - 150% of the pigment weight), Tego Dispers 750W, Lubrizol W150, Convey CT12, and Convey MT02. Other commonly used dispersants can also be employed in the present disclosure, and the listed dispersants are not exhaustive. Optionally, hyperdispersants such as Lubrizol W100 can be selected, and the dosage range is 20 - 150% of the pigment weight.

[0124] The dosage of the wetting agent (such as Surfadol TG) can be 10 - 100% of the pigment weight. The wetting agent can also be other surfactants that can improve wettability. In addition, a leveling agent such as polyethylene oxide N12K (PEG 1000000) can be used in a weight ratio of 0.01 - 0.1%. Any combination of the above substances can be adopted in at least one embodiment of this application.

[0125] The following are examples of pigment dispersions that can be used in this system: Example 1: Irgazin Orange 2% weight / volume (w / v), containing 15% pigment weight (wop), TEGO Dispers 755W, 0.05% w / v Polyox N12K;

[0126] Example 2: Sicopal Yellow 2% w / v, containing 3% wop Lubrizol W100; Example 3: Navamin Carmine 2% w / v, containing 100% wop Surfadol TG, 30% wop Lubrizol W100, 0.1% w / v Polyox N12K; Example 4: Unifast Blue 2% w / v, containing 20% wop Surfadol TG, 20% wop Surfadol XL167, 0.05% w / v Polyox N12K; Example 5: Iron Oxide Black 1% w / v, containing 100% wop Lubrizol W100, 10% wop Surfadol XL167, 0.05% w / v Polyox 308; Example 6: Iron Oxide Black 1% w / v, containing 10% wop Surfadol TG, 30% wop Surfadol XL167, 0.05% w / v Polyox 308; Example 7: Roman Black 2% w / v, containing 50% wop Surfadol TG;

[0127] Example 8: Grape Black 2% w / v, containing 100% wop Tego dispers 755W, 0.05% w / v polyox N12K; Example 9: Prussian Blue 2% w / v, containing 175% wop Tego Dispers 755W, 0.05% w / v Polyox N12K; Example 10: Pre-reduced indigo 60% (KraftKolor), containing 55% wop Tego Dispers 755W.

[0128] The above examples are not exhaustive, and other pigments and dispersion additives can also be used. Preferably, the amount of additives is minimized to improve the efficiency of the drying or heating process and reduce the possibility of active substances entering the plasma generation region of the module.

[0129] In another embodiment, the pigment can be dissolved in a solvent and applied to the article through a spray applicator. The solvent can be evaporated by a heating section, causing the pigment to precipitate on the surface of the article.

[0130] Figure 5A and 5B It includes a plurality of circular electrodes. The reaction gap 110 is the center spacing of the circular electrodes 100, since plasma can be formed between the electrodes 100 with opposite polarities. According to the plasma characteristics to be formed, the target coating, or the electrode cooling / plasma temperature requirements, other electrode cross-sectional shapes can also be used. The cooling system 45 can be used in conjunction with the electrodes 100 to cool the sheath and / or the core to the target temperature range. This helps reduce damage to the article 1 being processed. The cooling system can be configured to communicate with the fluid channels 108 of the electrodes 100.

[0131] A bias voltage 120 can be provided below the article 1 to attract the article and / or the fluid from the module 20 towards the article 1. The bias voltage can also be used to impart a visual effect to the plasma region 112. For example, the bias voltage forms a more homogeneous plasma, or even a more uniform plasma, to promote more ideal coating formation. The bias voltage can be an electrical bias voltage, such as a DC bias voltage or an AC bias voltage.

[0132] The method for processing the article 1 can include: providing a polymer formed by plasma polymerization to an article having a sheet-like or planar form. At least one fiber or yarn to be processed by the system 10 can be exposed on the surface of the article 1. The polymer can be formed by a plasma under atmospheric pressure, where the energy of the plasma is sufficient to initiate monomer polymerization and subsequent binding of the polymer to the article 1. The thickness of the polymer coating applied to the article 1 depends on the plasma density, the coating time, and the volume of the monomer introduced into the plasma region.

[0133] In another embodiment, the carrier fluid and the atomized material can be delivered to the chamber through a delivery system 40 and dispersed into the chamber through a diffusion plate (not shown). The diffusion plate can be disposed above the electrode 100 to enable the gas to be more evenly distributed to the electrode 100 at a substantially uniform velocity. This configuration can reduce the dot coating phenomenon caused by pressurizing the gas using the gas outlet 116.

[0134] In another embodiment, the module 20 can be configured with a series of lasers or other sensors for identifying the position of the article below the module 20. When an article is detected below the module 20, the electrode directly above the article 1 can be selectively activated to form the desired plasma. This is of particular value as it is not necessary to start or energize the entire module 20, since resources such as power, plasma gas, monomers, and pigments can be conserved because these resources are not provided in the regions not directly above the article 1.

[0135] Another embodiment provides a method of depositing a pigment on an article 1, comprising the steps of: atomizing a colloidal solution (or suspension) containing the pigment, introducing the solution into a plasma region, and depositing the pigment on the surface of the article 1 in an atmospheric pressure plasma environment.

[0136] The pigment can be small molecule aggregates or particles composed of hundreds to thousands of atoms, with a size range of 1 nanometer to 1000 nanometers, more preferably about 200 nanometers to 1000 nanometers. The carrier fluid can also deliver larger particles, either by monomer bonding or in the form of aerosolization, vaporization, or evaporation of the monomers.

[0137] The power supply 30 can be a generator or other mains power supply device for supplying power to the system and its components. For example, the power supply can be connected to the processing module within the chamber 15. The cooling system 75 can also cool the system during operation, particularly for cooling at least one of the processing module 20, the electrode 100, and the bias plate 120. The article can be supported by a support mechanism 80 with a bias 120 disposed below it. The bias can be a DC bias (or AC bias) and other electrical biases for controlling the plasma and / or guiding the particle flow in the plasma region 112. This can further promote the flow of the polymerizable monomers and / or the contained pigments towards and deposition on the article 1.

[0138] The system 10 includes at least a pair of electrodes 100 for igniting or exciting a plasma gas to form a dielectric barrier discharge plasma. The space between the electrodes 100 is called the reaction gap, where the reaction of the voltage with the plasma fluid, or the polymerization or cracking phenomenon of monomers or polymers can be observed. As Figure 5BAs shown, monomer cracking occurs within the plasma region 112, which may be located above, below, or between the electrodes. The molecules formed from the monomers after cracking flow along the ejection direction or the direction of the local electric or magnetic field, preferably towards the article, whereby the cracked molecules recombine to form a polymer that is preferably crosslinked or highly crosslinked, and then form chemical or physical bonds with the article 1. The plasma region 112 is formed within the reaction gap 110 and may fill the entire reaction gap or a part thereof. The distance between the electrodes 100 can range from 1 to 12 millimeters according to the required plasma density, and this distance is the reaction gap 110. The distance between the electrodes 100 can be the distance between the sheaths of adjacent electrodes 100 or the center distance between adjacent electrodes 100. It should be noted that if the sheath distance is used, the core distance will be larger.

[0139] A typical feature of dielectric barrier discharge is the presence of at least one dielectric barrier layer, such as the sheath 104, and the reaction gap 110 located between the corresponding electrode pairs 100. Dielectric barrier layer discharge can break chemical bonds, excite atomic and molecular particles, and generate active particles, such as free radicals. A dielectric barrier layer discharge system can be referred to as a "non-thermal system", "non-equilibrium system", or "cold plasma system".

[0140] Different from the "non-thermal system", in a thermal plasma, the temperatures of electrons and heavy particles are the same, so they are in thermal equilibrium with each other. In a non-thermal plasma, the ions and neutral particles (heavy particles) usually have a temperature lower than that of the electrons. Since the temperature of the heavy particles in the plasma remains relatively low, avoiding any undesirable polymer degradation, dielectric barrier discharge devices are considered suitable for polymerization and deposition processes. Compared with traditional thermal plasma systems, the inherent advantage of dielectric barrier discharge systems is that non-thermal plasma conditions can be easily achieved at atmospheric pressure or near atmospheric pressure and can be used to process or polymerize monomers and / or polymers.

[0141] The plasma can be generated by the discharge between the electrodes 100, where the plasma gas is excited or ionized to form the plasma. Any predetermined method can be used to generate the plasma, including: alternating current (AC) excitation, direct current (DC) excitation, low-frequency excitation, radio frequency excitation, and microwave excitation methods. The above methods can all be used to generate atmospheric pressure plasma. "Atmospheric pressure plasma", also known as normal pressure plasma, refers to a plasma with a pressure approximately equal to atmospheric pressure. It should be noted that even if the chamber 15 is filled with the required local atmosphere, its pressure is still approximately the same as the external environment of the chamber 15. In at least one embodiment, the internal pressure of the chamber is about 1 to 5 bar, but other pressure values higher than 1 bar can also be used.

[0142] Since the plasma module 20 can be used in an ambient atmosphere, the carrier fluid that generates the plasma in the reaction gap 110 can be pumped into the region between the article 1 and the module 20 and maintained for a predetermined time, so as to exclude the ambient gas in this region before igniting the carrier fluid and avoid the ionization or activation of ambient gas molecules. The region between the article 1 and the module 20 can be referred to as the "local region". If the system 10 is used in a closed chamber, it is also necessary to purify the ambient gas to control the functional processing characteristics. For example, the purification chamber 15 can remove oxygen in the chamber 15 that may react with monomeric substances or polymeric substances.

[0143] At least one additional fluid can be provided to the plasma region 112, which is carried by the carrier fluid or directly injected into the plasma region 112. This additional fluid is generally used to process the substrate 1 or apply a coating. In one embodiment, the additional fluid can be a monomer that can be polymerized in the plasma region for plasma-enhanced chemical vapor deposition (PECVD). Optionally, the additional fluid is supplied to the plasma module 20 through at least one additional inlet. If the carrier fluid and at least one additional fluid are provided to the module 20 simultaneously, it is preferable to mix the fluids in a predetermined ratio to ensure that a quantitative additional fluid can be transported to the substrate 1 through the outlet.

[0144] The monomer can be injected into the plasma chamber 15 in the form of a liquid spray, vapor or atomized particles, which helps to form ideal plasma conditions because it can stabilize the plasma streamer or plasma corona conditions formed in the reaction gap 110. Stabilizing the plasma conditions means forming a plasma glow or a stable plasma in the reaction gap 110. It should be noted that the voltage and frequency applied to the electrode 100 also contribute to maintaining and / or forming a stable plasma.

[0145] In another embodiment, if the article 1 is a substrate, the plasma can only process the first side of the substrate, while the second side of the substrate can be protected by treatment, or can be separately treated by different films or treatment processes. This allows for the selective modification of one side of the substrate. The protection of one side of the substrate can be achieved by applying a protective film / protective layer to the second side of the substrate, or by pressing the second side of the substrate against a surface that prevents the coating or treatment from being applied to the second side of the substrate.

[0146] The power supply 30 may include more than one power supply unit. The power supply 30 may be connected to respective modules 20, enabling the system user to start, stop, change, or manipulate the modules 20 according to processing requirements. Each module in the system may have a unique and separate power supply 30, which can be started as needed. Alternatively, the power supply 30 may be used to power one or more modules and / or components of the system 10. The power supply 30 may be a radio frequency power supply for powering a radio frequency electrode, or may be an AC (alternating current) power supply or a DC (direct current) power supply 30. The electrode 100 may be composed of a core 102 and a sheath 104 covering the core. The core 102 is formed of a conductive material, such as copper, gold, or stainless steel, and the sheath 104 is preferably formed of a dielectric material, such as glass or alumina. The core 102 is preferably a conductive material that can resist a temperature equal to or less than that of the plasma formed in the plasma region. The sheath 104 is selected as a dielectric material that can coat or encapsulate the core 102 to reduce arcing and stabilize the plasma formed in the reaction gap 110. Optionally, a fluid channel 108, such as an air gap or a liquid gap, may be provided around the core 102, which helps in the cooling of the electrode 100 and its dielectric properties. For example, air or an inert gas may be used as the cooling fluid, passing between the electrode core 102 and the sheath 104. In another embodiment, the electrode 100 may be configured with one or more fluid cooling channels or a single cooling channel for cooling the electrode 100. Optionally, a fluid channel may be provided inside the core 102 through which fluid can pass to cool the electrode 100.

[0147] The electrode sheath 104 may be rectangular or circular, and the core 102 may be of any predetermined shape, which may or may not correspond to the shape of the electrode sheath. For example, the electrode 100 may be a blade-type electrode 100 having a rectangular sheath cross-section, but the core may be circular or any other predetermined shape. The fluid channel may have any predetermined cross-section, including regular shapes, sinusoidal waveforms, or wavy cross-sections. The overall shape of the sheath 104 may define the type of the electrode 100, regardless of the cross-section of the core 102. However, matching the shape of the core 102 to the shape of the sheath 104 may have certain advantages.

[0148] Since the present system operates as an atmospheric pressure plasma system, the chamber 15 can operate without a vacuum pressure. The cleaning, functionalization, and activation of the article 1 can be achieved through different plasma treatment methods and plasma exposure. In ambient air, the functionalization can impart groups including at least one of: oxygen-based, nitrogen-based, and hydrogen-based groups. In another embodiment, the plasma can be used to etch the surface or modify the surface by removing substances from the surface.

[0149] If the surface is activated, reactive groups may be present on the surface, which can form a better bond with the particles that interact with the surface. In another embodiment, the pigment may be activated by plasma, which can be achieved directly by forming physical bonds or through reactions occurring on the surface of the pigment.

[0150] Contaminants passing between the chambers can be driven towards the suction locations, and one or more such suction devices can be configured in each of the chambers 15A - 15C.

[0151] The suction locations can be directed to an exhaust system or a recirculation system 70. If the contaminants are introduced into the recirculation system 70, the contaminants can be purified. The purification can include at least one of the following stages: combustion stage, cooling stage, heating stage, capture stage, and exhaust stage. Each stage can be used in combination with each other or implemented in any desired manner, and multiple identical stages can be applied to the recirculation stage.

[0152] Collection and recirculation within the chamber 15 can be achieved through the suction locations. Multiple suction locations can be provided around the system for sucking fluids and by - products that need to be discharged from the system chamber 15. Filtration can be performed to separate larger particles from the collected by - products and gases, and smaller particles can be transported downstream for collection, purification, and / or removal. For the recirculation system 70 that receives fluids and particulate products from one or more suction locations, the filtration stage can be the first - stage separation process.

[0153] Preferably, a cryogenic cooling stage is employed to freeze some of the contaminants and enable the plasma fluid to be reused in the process. The cryogenic cooling stage can be a cryogenic separation process that separates argon from other gases and particulate contaminants through a heat exchanger and a separation column. Gas compression can be performed at the inlet of the recirculation system. The gas feed stream to be recirculated can be cooled and preferably partially liquefied. The separation of nitrogen, oxygen, and argon can be achieved through this cryogenic separation process. In some embodiments, gaseous nitrogen and oxygen can be separated from liquid argon and then can be reinjected into the system, stored, or discharged.

[0154] In another embodiment, other contaminants may be incorporated into the recirculated gas, and these contaminants may undergo reliable combustion or reaction with other impurities in the recirculation system. Such substances may include oxygen, nitrogen, and / or hydrogen. Preferably, the contaminants removed from the recirculated gas stream are water and carbon dioxide, but siloxanes, pigments, solvents, solutions, alcohols, and other contaminants may also be captured and disposed of in a desired manner. It should be understood that the polymerization chemical agent to be used will be the main source of pollution, and the pigments and solvents / solutions used in the pigment application process will also constitute contaminants. Therefore, the system by-products can only be determined when specific colorants are selected, and the recirculation process can be adjusted to meet specific recirculation requirements. However, preferably at least the purified plasma gas is returned to the system for subsequent processing use. Since the recovery rate cannot reach the optimum, supplementary plasma fluid can also be included in the recirculated plasma gas.

[0155] In addition, it is preferred to return the purified gas to the system at a desired temperature for subsequent product processing. The temperature range of the plasma gas, such as argon, should preferably be controlled between about -30°C and 40°C.

[0156] More than one suction position may be provided in the chamber 15, and each suction chamber is configured to filter at least one of the incoming gas and particulate matter. The gas, particulate matter, and other fluids entering the suction position can be transported to the recirculation system 70.

[0157] The pigment applicator in the first chamber 15A is preferably any device capable of supplying or applying pigment to an article. The pigment may be in a dry state, contained in a binder, dispersed in a dispersion, present in a solution, or dissolved in a solvent when applied. More than one pigment and pigments in different states can be applied to the article in the first chamber 15A. The pigment applicator can be arranged as shown Figure 1 above the article relative to the position, or may be arranged parallel to the movement direction of the article 1 as shown in Figure 2.

[0158] The vertically arranged pigment applicator may be provided with a collection trough or a suction position below the pigment applicator, so that the fluid in the applicator can be vertically ejected onto the article 1. The excess fluid and / or pigment that is not attached to the article from the applicator can flow to the suction position under the action of gravity. The pigment applicator can eject the fluid in any suitable manner, and can eject the fluid in a straight line or in a fan or arc shape towards the article. The pigment applicator can be arranged in any desired orientation, and the distance from the surface of the article 1 can be set to 1 mm to 500 mm.

[0159] More than one applicator can be provided within the chambers 15, 15A. The pigment applicator can also be provided on both sides of an article, such as a substrate, so as to achieve two-way coating of the article. In addition, providing more than one pigment applicator can apply more than one type of pigment on one or more surfaces of the article 1 simultaneously, or the same pigment can be applied on both sides of the article to achieve multi-sided pigment coating.

[0160] The pigment can be a colorant and / or a functional pigment applied to the article 1. Dye pigments can also have certain functions as needed. For example, colorants formed from metal oxides can have functional properties suitable for antiviral or antibacterial treatments, such as the case of copper oxide pigments.

[0161] Some pigments with corrosion resistance can be selected, such as corrosion inhibitor pigments (CIP), which can allow fluids, such as water or air, to diffuse, thereby dissolving or partially dissolving the pigment. Certain pigments can have a higher or lower pH value, which is beneficial for different environments and corresponding corrosion resistance. Preferably, CIP is composed of metal ions, and the metal ions can be derived from metal cations such as zinc, copper, titanium, brass, strontium, chromium, lead, molybdenum, aluminum, calcium, and barium. Alternatively, the pigment can be an anion, such as anions derived from phosphorus (orthophosphoric acid and polyphosphoric acid), chromic acid, and boric acid.

[0162] Another optional pigment is a conductive pigment. These conductive pigments are at least partially composed of the following materials: copper, iron, silver, nickel, silver-plated nickel, carbon black, multi-walled and single-walled carbon nanotubes, and other materials.

[0163] Thermally conductive pigments can allow conductive properties and can improve heat conduction performance, which has significant advantages for flexible products and products that require heat conduction from the contact surface.

[0164] Optionally, the plasma coating used to fix the pigment on the article 1 can also have conductive properties, thereby ensuring that the pigment forms a conductive path or assisting in heat conduction. Conductive pigments can usually be applied in one or more layers, and their structure can be similar to a laminate. Each pigment layer can have unique pigments, fillers, binders, and / or particle sizes. The differences between the laminates can also endow the laminate with the required functional properties, which have practical value in battery applications.

[0165] Each laminate can be plasma-treated or a plasma coating can be applied to the pigment to construct the laminate. Regardless of the number of laminates, the overall structure can be referred to as a coating, and preferably a plasma coating, because multiple layers or laminates are plasma-treated.

[0166] Conductive pigments can also be used for electromagnetic shielding and can be arranged on the surface of the article in a predetermined pattern or array, thereby achieving selective conductivity or electromagnetic blocking or shielding.

[0167] In another embodiment, the conductive coating can be composed of a conductive pigment and a non-conductive resin binder. The binder binds the pigment, while the conductive filler provides a conduction path. Charge is transported through the conductive filler and, if necessary, short-range jumps occur in the matrix between the particles.

[0168] The pigments in such coatings are preferably in the form of flakes, plates, tubes or strips, but pigments of any geometric form can also be used as required. Carbon powder, nickel flakes, silver-plated copper flakes and silver flakes can be used as pigments in such coatings. The filler of the coating is preferably a carbon-based material, as it is usually cost-effective and suitable for conductive applications, grounding applications and electromagnetic shielding applications. When high conductivity and / or high-frequency electromagnetic shielding are required, silver-based pigments are preferred.

[0169] In another embodiment, the pigment applied to the article 1 can include ferromagnetic powders, such as Fe-Co, Fe-Co-Ni, Fe-Co-Co-Ni, Fe-Co-B, Fe-Co-Cr-B, Mn-Bi, Mn-Al, Fe-Co-V alloys, bronze powder and other transition metal alloys.

[0170] The binding of the pigment is preferably achieved through a plasma polymerization coating formed by the module 20. This plasma polymerization coating can determine the adhesion, durability, chemical resistance and feel characteristics of the coating. Preferably, the polymerization coating is applied so that the pigment applied by the pigment applicator can be fixed to the article. The coating can also preferably have one or more functional characteristics that are generally in common demand in the electronics, energy storage and / or clothing industries.

[0171] After the pigment is applied to the article 1, the article 1 is then processed by the plasma processing module 20. The plasma processing module 20 can be configured to polymerize monomers or precursors that are a pigment solution or solvent. Alternatively, the plasma module 20 can be configured to supply monomers and / or precursors to be polymerized to the plasma region, thereby forming a thin film or coating on the pigment provided by the pigment applicator.

[0172] The plasma generated by the plasma module 20 can be a glow plasma, which can be formed under atmospheric pressure or near-atmospheric pressure conditions. Conventional plasma systems usually require a vacuum pressure chamber to generate a glow plasma, while this system is adapted to generate a glow plasma in the pressure range of 95 kPa to 110 kPa. Preferably, the internal pressure of the chamber 15 is maintained in the range of 99 kPa to 102 kPa, so that the internal pressure of the chamber is substantially the same as the external atmospheric pressure, thereby reducing the infiltration of fluid into the system and the spillage from the system respectively.

[0173] The intensity of the glow plasma can be regulated by the flow rate of the plasma gas, Penning ionization gas, Penning ionization chemical agent, or the voltage applied to the electrodes of module 20. The electrodes 20 can be arranged in an array to form a plasma plane or axis, thereby defining the plasma region of the module. Multiple positive and ground electrodes can be employed within a single module 20, and the electrode surface spacing where plasma is generated therebetween ranges from 1 mm to 12 mm. Dielectric barrier discharge (DBB) can form a discharge phenomenon between two electrodes separated by an insulating dielectric.

[0174] Preferably, the electrode consists of a conductive core and a dielectric barrier sheath that coats the conductive core. The thickness of the dielectric layer can be from 0.1 mm to 6 mm, and the thickness of the electrode core is from 0.1 mm to 6 mm. The conductive core can be circular, and the core diameter ranges from 0.1 to 6 mm. Optionally, a coolant channel can be provided inside the core for the circulation of coolant to cool the core and sheath that constitute the electrode.

[0175] The treatment of articles such as textiles is usually limited by their heat-resistant temperature. Therefore, it is preferred that the temperature of the plasma is cold plasma, or the plasma has a temperature below approximately 200 °C at any position in the plasma region where it may contact the article. The parameters that can be regulated by this system include: plasma gas type, residence time of the plasma gas and active components, flow rate of the plasma gas and active components, frequency, power, pressure, ambient temperature, aerosol, vapor, electrode spacing, bias plate, and the temperature of the gas, monomer, and electrode.

[0176] The module 20 can be powered by an alternating current radio frequency power supply or a direct current power supply. Different power supplies have different effects on the formation of the plasma, the pulse of the plasma, and the total energy required to initiate and maintain the plasma. The module 20 can be configured with a starting device that excites the plasma gas to form plasma through high-energy input and then maintains a stable or ideal plasma state with lower energy input. The starting device can be integrated with the power supply or externally connected to the power supply. Compared with maintaining the plasma, the voltage required for the starting process can reach 1.5 to 10 times the plasma ignition voltage.

[0177] The voltage range required for the electrode can be a primary voltage of 20 V to 80 V and a secondary voltage of 1.5 kV to 6 kV. The power requirement per unit area of the plasma is 0.1 W / cm 2 to 2 W / cm 2 , but it should be understood that the overall geometric structure of the module 20 and the electrodes will affect the plasma region and the final plasma density. The power output range of a single module can be from 500 W to 4500 W. It should be noted that the required power and voltage may vary depending on the plasma gas and the monomer or precursor to be polymerized.

[0178] A pulsed or duty cycle power supply can be employed to adjust the formation of plasma or the intensity of the plasma as needed. It is advantageous to control the duty cycle within the range of 5% to 60%, as it can form active substances in the plasma and act on the article, or an existing coating or pigment thereon, without generating undesired substances during the polymerization stage. The plasma module 20 can apply pulses to the plasma intensity, thereby controlling the deposition rate and the type of deposited substance within the plasma region before the substance is deposited onto the surface of the article 1.

[0179] The article can obtain a coating or a laminate when passing under the first module 20. Subsequent modules 20 can be used to apply additional coatings, additional laminates, and / or continue the coating applied by the first module 20. Any number of coatings can be applied to the article, and the spacing between the modules and / or between the module electrodes enables the coatings to be applied as independent layers, which not only helps to improve the durability of the final overall coating applied to the article but also further promotes the fixation of the pigment on the article 1.

[0180] Optionally, a laminate can be provided: apply a pigment after applying a plasma coating, and then apply another plasma coating on the pigment, so that the pigment is disposed between the plasma coatings / thin films. In this way, the pigment can be coated or embedded relatively deeper into the plasma coating, thereby fixing the pigment in the desired position. The system can provide any number of laminates.

[0181] A post-treatment module can be provided in the third chamber 15C or the chamber 15. The post-treatment module can be selected from the following group: heating element, grinding element, grinding roller, pressing roller, laser, sintering device, radiation lamp, electromagnetic radiation device, and exposure equipment. The above post-treatment devices can be used to enhance or complete the coatings applied in the first chamber and / or the second chamber.

[0182] More than one post-treatment module can be provided in the chambers 15, 15C, or it can be provided in an open environment outside the chamber for performing inspections during the final post-treatment step.

[0183] Although the article can be coated and finished or enhanced through post-treatment steps, the system 10 can be adapted to provide a coating to the article 1 such that the module 20 provides a fully or nearly fully plasma-polymerized coating with the required properties, such as fixing the pigment therein, without post-treatment processes.

[0184] A plasma coating refers to any coating formed by plasma, and plasma treatment is to use plasma to change or enhance the surface of the article or react with chemical agents coated on the article. It should be noted that plasma treatment can form a plasma coating through polymerizable monomers or precursors, and the monomers or precursors are already on the article or pass through the plasma from the manifold outlet before being deposited onto the article 1.

[0185] The plasma module 20 can be formed within a housing channel, where a supply manifold and at least a pair of electrodes are configured. The housing channel defines an open plane through which plasma gas and / or chemical agents can be delivered to the article. Preferably, the pair of electrodes is disposed near the top of the channel, while the manifold is disposed opposite below the electrodes.

[0186] Figure 2B Another embodiment of a system suitable for applying pigments to an article is shown. The pigment applicator shown sprays the pigment in a generally horizontal direction such that the article can pass vertically through. The planar article 1 is shown, which can be a textile substrate. In this configuration, the spraying of the pigment applicator can be more concentrated in a smaller area, thereby restricting the spread of excess pigment to a larger area. Additionally, a first pigment applicator can be provided on a first side of the substrate article, and a second pigment applicator can be provided on a second side of the substrate article 2. Optionally, a collection tray or similar collection device can be provided below the applicator 18 such that excess pigment is collected and does not fall on the article, where the article moves below the pigment falling under gravity. The collection tray can be connected to one or more suction locations for removing the pigment and the fluids adhering during its application or conveyance. In another embodiment, the article does not move below any pigment dripping or gravity falling location to avoid accidental contact of the article with excess fluid or pigment.

[0187] The plasma module 20 can be housed within the chamber 15 or exposed to the atmosphere, in which case local purging is required before exciting the plasma to ensure that a high-purity plasma gas is excited. The plasma module is preferably configured to provide chemical agents to the article 1 to be polymerized such that the pigment applied by the pigment applicator can be fixed by the plasma coating provided by the plasma module. This coating application method is original and can provide smaller particles to be polymerized compared to conventional methods (where the coating to be polymerized is applied and then conveyed to the plasma treatment area).

[0188] The method for applying the polymer coating to the article employed in this system is preferably the plasma-enhanced chemical vapor deposition (PECVD) method. This PECVD method can perform cracking before forming a recombinant plasma polymer on the target surface of the article 1. Compared to in-situ coating polymerization that attempts to introduce plasma polymerization, cracking can more effectively break chemical bonds, thereby allowing PECVD to use a wider range of chemical agents and precursors. Additionally, a stronger or improved bonding can be established between the article 1 and the thin film / coating formed during the PECVD process. Moreover, due to the inherent thickness limitation of the coatings applied during non-PECVD processes, the thickness of the coatings applied during non-PECVD processes, as its minimum coating thickness, typically increases significantly, and it is difficult to form a fully polymerized coating or a uniformly polymerized coating, and also has a generally weaker bonding with the article after polymerization. Therefore, the PECVD method has inherent advantages over traditional coating methods or post-plasma polymerization methods.

[0189] A higher power needs to be applied to the pre-coated coating to be polymerized to achieve effective polymerization of the coating. In addition, compared with the coating formed by the plasma polymerization technique in which the chemical agent first passes through the plasma region and then is deposited on the article, the coating thickness applied in the pre-coating method is usually larger. Therefore, compared with the plasma treatment module for polymerizing the existing chemical agent on the polymerized article, the plasma coating module can achieve a more complete polymerization effect with lower energy consumption.

[0190] Figure 3 Another embodiment is shown, which shows a plurality of pigment applicators and a plurality of plasma treatment modules. In this configuration, the first pigment applicator can apply a first pigment to the article. Subsequently, the article 1 is conveyed to the chamber 15, and the chamber 15 is provided with a plasma treatment module 20. The plasma treatment module 20 is adapted to polymerize the coating applied by the pigment applicator and / or form a polymerized film or polymerized coating containing the pigment on the article to fix the pigment in place. The combination of the pigment and the plasma coating can be referred to as the first plasma coating.

[0191] The second pigment applicator is disposed behind the first plasma module 20 and can be used to apply a subsequent pigment on top of the first plasma coating. The pigment can be applied to the first plasma coating in the same manner as the first pigment applicator, or can be applied using a different pigment applicator or method, because the first plasma coating can change the surface to which the pigment is applied compared to the surface of the article before treatment. It should be understood that the second pigment applicator can be functionally equivalent to the first pigment applicator and achieve the same pigment application effect.

[0192] The second pigment applicator can also be used to apply a second colorant, functional pigment, or any other predetermined pigment to the article and / or the first coating. The additional pigment can then receive a plasma coating thereon, whereby the plasma coating is the second plasma coating applied to the article 1. The thickness of the second plasma coating can be thinner than the first coating, the same as the first coating, or thicker than the first coating.

[0193] The first coating on the article can make the formation or construction speed of the second coating relatively faster than the first coating, because the first coating can serve as a base layer to enable any additional coating to have a faster deposition rate, especially when the plasma module is adapted to provide chemical agents for the deposition of the second coating.

[0194] In another embodiment, the first plasma coating applied to the article can be partially polymerized, so that the pigment applied by the second pigment applicator can react with the partially polymerized coating and can also be partially embedded or infiltrated into the partially polymerized coating.

[0195] In another embodiment, the system is adapted to apply pigments and / or coatings to a predetermined location on an article, and the second pigment applicator may also be configured to apply pigments and / or coatings to the same predetermined location or a second predetermined location. Thus, the system can be adapted to form patterns with variable colorants and / or variable functional properties. This technique is particularly applicable to flexible circuits, aesthetic pattern design, abrasion resistance improvement, grip improvement, or any other predetermined or desired pigment application.

[0196] In another application, the pigment applicator can be replaced by a hot melt applicator, which is adapted to form beads or three-dimensional arrays on an article. The hot melt applicator can be used to melt particles, pigments, pellets, etc. for the controlled application of elements to the article. The elements can be used for contact application and can have a plasma coating after application, or the elements can be cured by plasma treatment. The hot melt elements can be printed onto the article by the hot melt applicator and cured on the article. Optionally, the elements can include one or more pigments, which can be contained within the element or protrude from the element.

[0197] The elements can be extruded from the hot melt applicator and fixed to the article by curing. Plasma coating can be used to assist in the fixation of the elements. The elements can be chemically bonded to the article or can form a surface adhesion with a distinct interface.

[0198] Optionally, the system 10 can be adapted to process articles 1 in batches or to process a single article 1. The system 10 is adapted to apply a coating to an article through a process that includes a plasma treatment step.

[0199] The process of using the system can include applying pigments, powders, or particles to an article. The terms pigment, powder, particle, and nanoparticle can be collectively referred to as "particles", and the term "pigment" can optionally be replaced by the term "particle", i.e., in this context, pigments should be understood to include a broader range of particles.

[0200] In another embodiment, the system can be adapted to apply particles to an article in the form of a solution or solvent. Subsequently, the solution or solvent can be removed from the article, leaving the particles on the article 1. During the removal of the solution or solvent, the particles may migrate on the article due to the surface tension of the solution or solvent leaving the article. Heating, especially hot air flow or infrared heating, can be used to evaporate the solution or solvent on the article 1, keeping the particles substantially in the applied position or causing the particles to enter the recesses of the article 1. This can prevent particle agglomeration or migration to unintended areas of the article 1, thereby improving the uniformity of particle distribution on the article 1.

[0201] The article can have a natural surface charge, which can be temporarily changed to promote the adsorption of microparticles to one or more desired surfaces of the article 1. The change in the surface adsorption can be achieved by an electrostatic field, a magnetic field, applying a charge to the article, or friction to generate a negative charge on the desired surface of the article. The change in the surface charge is preferably temporary, but can last for at least part or even the entire processing process, so that the pigment can be temporarily fixed in place before the plasma polymerization coating is formed around and / or on the surface of the pigment.

[0202] The pigment applicator of the system can include one or more different mechanisms for achieving the dispersion and application of the pigment on the article 1. The pigment is preferably stored in a storage bin or hopper and is transported to the application head through a manifold. Subsequently, the pigment can be distributed on the article by a variety of different methods.

[0203] The dispersion method depends on whether the pigment is in a suspension or dry pigment is applied to the article. The distribution method can include using a carrier fluid, such as a gas or a liquid, which can be used to transport the pigment to the article. The gas used to transport the pigment is preferably an inert gas, or a gas that is beneficial to the plasma polymerization process and beneficial to the formation of active substances in the plasma generated in the plasma processing module 20.

[0204] Optionally, the pigment applicator can form part of the plasma processing module 20, so that the pigment applicator passes the pigment and the carrier fluid through the plasma before the pigment is deposited on the surface of the article. Applying the pigment in this way, the pigment can be excited and combined with the binder, chemical agent, precursor, monomer, or other pigments. When the pigment and the carrier fluid are transported from the outlet of the pigment applicator to the plasma region, the excitation and / or combination of the pigment with the precursor, chemical agent, or monomer can be achieved.

[0205] It should be understood that the carrier fluid may not form part of the reaction in the plasma region when it is part of the intended polymerization process, but can be used to react with substances in the plasma region that are not desired to be deposited on the article 1. Any by-products generated by the system can be gases or microparticles, and these gases or microparticles can be directed to the suction position in the system chamber 15 for recycling or disposal.

[0206] In one embodiment, the pigment applicator is adapted to apply powder to the article electrostatically. In this configuration, the pigment supplied to the pigment applicator is connected to an electric current and charged, and then the charged particles are ejected or distributed from one or more outlets facing the article. The pigment can then be adsorbed onto the article and fixed by a subsequent plasma coating. The pigment used in this method can be a mixed pigment, where some pigments include colorants and other pigments are for functional purposes. The functional purpose can be to endow the article with terminal functional characteristics, or it can be a functional characteristic to assist the electrostatic coating method of the pigment applicator.

[0207] For an auxiliary coating method, it is desirable to apply an electric charge to the article or the peripheral region of the article to enhance the pigment adsorption effect. This can be achieved by applying an electric charge to the article, or by forming an electric field, an electrostatic field or an electrostatic region around the article to provide an attractive force to the article. A base or a rechargeable element can be provided relatively below the article to generate the required electric charge in the article region. Preferably, the article is grounded or has an electric charge opposite to that of the pigment.

[0208] The pigment coating can employ pigments formed from a polymer resin, which can be combined with at least one curing agent, leveling agent, colorant, flow modifier or other additives that impart functional properties to the coating. The combination of these components can be achieved by melting the composition, cooling the melt and then grinding the cooled mixture into a powder, which can be referred to herein as a pigment. Such pigments can be ground to any desired size and preferably contain a binder that can undergo polymerization or reaction upon exposure to a plasma region.

[0209] Different from traditional powder coating systems, the present system 10 and method preferably employ a plasma treatment step in the chambers 15, 15B. The plasma treatment module can be used to cure, react, melt or otherwise fix the pigment to the article such that the colorability of the pigment can still be manifested after the plasma treatment. Optionally, the plasma treatment can be a plasma coating step, whereby an additional chemical agent is applied to the article that has received the pigment coating. The additional chemical agent can be a chemical agent suitable for polymerization upon exposure to a desired plasma state, such as a glow plasma, or is adapted to react with at least one additive or curing agent of the pigment applied in the electrostatic application step under plasma exposure conditions.

[0210] Optionally, after the plasma treatment or coating step, at least one post-treatment step can be performed on the article and the coating thereon, including at least one of a cooling step, a heating step, a grinding step, laser exposure, sintering, electromagnetic radiation and / or light irradiation steps to complete the coating on the article. The post-treatment can be implemented in the same chamber 15 as the plasma treatment and / or plasma coating, or can be performed in a separate chamber 15C.

[0211] The output voltage range of the electrostatic device can be from 5 kV to 100 kV, but in some configurations, the output voltage can be reduced according to different pigment types or sizes.

[0212] The fluid pressure range of the electrostatic pigment applicator can be from 0.5 CFM to 20 CFM, depending on the pigment size and the distance from the article. Optionally, a series of discrete applicators can be provided in the width direction of each applicator 18 for selectively applying the pigment on the article 1. The fluid used to drive the pigment out of the pigment applicator can be any compressible predetermined gas, which can be the same as the plasma gas used in the plasma treatment step of the system, or can be a fluid capable of forming reactive species in the plasma region. For example, the fluid can be nitrogen, air, oxygen, carbon dioxide, or other desired reactive gases. Alternatively, inert gases such as helium, argon, neon, xenon, etc. can be used. If the inert gas is different from the plasma gas, the inert gas provided in the pigment application step can promote plasma generation in the plasma treatment step due to the inert gas being transported to the plasma region of the plasma module.

[0213] Optionally, the article can enter a fluidized bed, where the heated article passes through the pigment bed layer. Thus, the heat of the article can be supplemented by additional heat sources in local areas of the fluidized bed, which is sufficient to melt or react the pigment in the bed layer, causing it to adhere to the article before the plasma treatment step.

[0214] In another embodiment, the pigment applicator can be adapted to be a five-axis applicator, or a six-axis applicator can be used for more complex articles to be processed, so that the pigment can be applied to the article from any desired direction or at any desired distance. This configuration is beneficial for controlling the particle flow and the thickness of the applied pigment coating.

[0215] For roll-to-roll processed articles, it is generally preferred to use a fixed nozzle to simplify the processing flow, but when a specific effect needs to be applied to the coating, the pigment applicator can be adapted to be mobile. For example, by axially moving the pigment applicator in the width direction, the pigment can be prevented from adhering to some areas of the article.

[0216] The outlet size of the mobile pigment applicator can be relatively smaller than the article to be processed, so as to control overspray or unintended application of the pigment during movement. The outlet of the pigment applicator can be of any predetermined shape, but preferably circular, oval, or rounded shapes are used to assist in achieving controllable pigment application.

[0217] A spray curtain or jet curtain can be part of the pigment application process and can be referred to as a spray applicator. The spray applicator can be composed of one or more spray nozzles or jet devices. The spray applicator can have a series of outlets arranged in a predetermined manner so that a curtain or wall of pigment application spray, aerosol, vapor or other propellant can be ejected from the spray applicator. When ejected from the outlet, the temperature range of the fluid and / or pigment from the spray applicator is about -50°C to 280°C. The specific temperature range can be restricted according to the characteristics of the article to be processed to ensure that the article is not damaged during processing. Although the ejection temperature may be higher or lower than the ambient temperature, when the fluid and / or pigment contacts the article 1, its temperature may have been cooled or raised to allow the fluid and / or pigment temperature to be higher or lower than the acceptable temperature tolerance of the article to be processed. For example, the melting point of polyester is about 260°C, and the temperature of the fluid and / or pigment ejected from the spray applicator is about 280°C, but the desired cooling effect can be achieved by controlling the distance between the outlet of the spray applicator and the polyester article, so that the temperature of the fluid and / or pigment is reduced to a level lower than the melting point temperature of the polyester article.

[0218] It should be understood that the system will be adapted to limit the minimum and maximum temperatures of the pigment applicator to prevent damage to selected types of articles before processing. Alternatively, the system can have an article material identifier to automatically detect the material to be processed and implement dynamic temperature control.

[0219] In addition, the system can be adapted to determine the thickness of an article, such as a substrate, and adjust the relative position of the surface to be processed with respect to at least one of the pigment applicator and / or the plasma module and / or the post-treatment module. The determination of the article thickness can be achieved by virtual measurement techniques, that is, by generating a virtual box to determine the height profile of the article to be processed. Such a system will use a camera system to evaluate at least one of the height, width, topography and porosity of the article. Based on these measurement data, the compression amount of the inlet pressure roller can be changed or modified, so as to achieve the desired processing speed while reducing the unexpected tension on the article 1.

[0220] When the chamber gas contains one or more recyclable plasma gases, the gas can be purified. For example, argon can be collected and reused, while by-products and contaminants are removed from the collected gas so that the gas can be returned to module 20 for reuse at a purity of about 95% or higher.

[0221] The system 10 can adopt an electrostatic transfer drum (ETD) system. The ETD system can be used to apply one or more colors in any predetermined pattern, array or shape. Preferably, the ETD transfers one or more colors across the entire width of the article to be processed, but some designs or patterns can also be limited to a predetermined image to be reproduced according to requirements.

[0222] The image to be reproduced by ETD can be projected onto the photosensitive surface of the xerographic plate to form an electrostatic latent image thereon, and then the latent image is developed to form an electrostatic powder image corresponding to the latent image on the plate surface. Thus, the application or transfer of one or more colors, the application or transfer of many colors, and the application or transfer of any desired pattern or shape can be achieved. The powder image can then be electrostatically transferred to the carrier surface and fixed by a fixing device and then transferred to the article 1.

[0223] The excitation device or lamp group can be positioned or directed towards the xerographic plate and / or the article 1. The excitation device can have a plurality of independent lamps, and the excitation of the lamps can cause the image of the relevant color to irradiate the photosensitive surface of the xerographic plate in the exposure area. The plate can be a flexible photoconductive belt assembly. The photoconductive belt assembly can be installed such that the light imaging rays for applying the original or desired image are continuously flashed onto the surface of the belt. The belt structure preferably uses a material that can be sensitized by a corona generator or other charge application device before exposure.

[0224] After the surface of the belt is irradiated by the light image, the photoconductive layer discharges in the light-receiving area, so that the electrostatic latent image remains on the belt. As the surface of the belt continues to move, the electrostatic latent image passes through the developing station. The developing station can include one or more devices with color developing materials for selectively developing the electrostatic image. The continuously developed electrostatic image is then conveyed by the belt to the transfer station to complete the transfer to the article. After the image on the belt is transferred to the article, the article with the image can be subjected to plasma treatment or a plasma polymerization coating can be applied to it. The plasma treatment can also form a plasma polymerization coating on the article 1.

[0225] In another embodiment, the article 1 can be conveyed to the fixing assembly to permanently fix the transferred powder image on the article 1. After fixing, the image can be irradiated with white light and then conveyed to module 20 for plasma treatment or plasma coating. It should be noted that the image can include one or more colorants, which are transferred to the article 1 during the processing to achieve the desired coloring effect of the article. This has special value for article printing or applying a uniform color or pattern on the article 1.

[0226] The system can also use a laser-like printing device. Such a device can use static electricity to charge or give the article 1 and / or the pigment adsorption characteristics. Static electricity is essentially the charge accumulated on insulators such as balloons or the human body. Due to the attraction of oppositely charged atoms, objects with opposite electrostatic fields will adhere to each other. Laser printers use this phenomenon as a "temporary adhesive". The core component of its system is the photoconductive drum, usually a rotating drum or cylinder. The drum assembly is made of a high photoconductive material and can be discharged by photon irradiation.

[0227] In another embodiment, the system 10 may further include a brushing device for urging the pigment of the article 1 into or into the depths of the recesses on the surface of the article. The brushing device may have one or more bristles or elongate elements for moving the pigment. Alternatively, the pigment coating may be redistributed by rubbing the surface of the article or pressing against the surface of the article with a textured abutment device to achieve a uniform coating thickness and / or to redistribute the colorants of the pigment coating before entering the plasma region. For simplicity of description, the rubbing and textured abutment devices are collectively referred to as the brushing device, but any of the foregoing designations may also be used according to their respective predetermined functions.

[0228] Moving larger-sized pigment from the upper surface region of the article to the recesses on the surface of the article can also improve the plasma coating to be applied. The improved plasma coating may include: better embedding or fixing of the pigment to be fixed through the plasma coating or, when the pigment and a polymerizable binder are applied to the article together, through the plasma process. For example, larger pigment applied to the article may more easily enter any recesses in the article.

[0229] Urging the pigment into the recesses can also form a defined pattern, where the recessed areas are darker in color and the higher parts of the article are relatively lacking or completely free of pigment coverage. By using this method, the pigment can be mainly distributed in the recesses of the article, so that the upper surface area of the article is basically free of pigment coverage. This is advantageous when two or more pigments are applied, as it also enables control of the coloring of the recesses and / or the upper surface of the article.

[0230] The brushing device may form a seal or partial seal with the article, thereby reducing the infiltration of pigment from the coating chamber of the system into the plasma processing chamber of the system.

[0231] If the coating chamber and the plasma chamber are the same chamber, the brushing device may be used to introduce excess pigment and / or pigment solution on the surface of the article into a collection container. When there is contamination or cross-contamination of multiple different colored pigments, the pigment and / or solution in the collection container can be recycled or disposed of. Optionally, a fluid stream or fluid jet may be used to urge the pigment out of the recirculation or recovery stream, thereby removing it from the system or collecting it for disposal.

[0232] In another embodiment, the system 10 may employ a powder dispenser or a sieve to achieve uniform distribution of particles on the article. The powder dispenser or the sieve may be used to apply pigments of a predetermined size or smaller to the article. The powder dispenser or sieve-type pigment applicator may be disposed at a position relatively above the article to achieve gravity application. In another example, the system may employ a fluid stream to direct the pigments falling from the sieve onto the article to be processed to apply at least one of the pigments and / or the plasma polymerization coating. The pigments that do not meet the requirements in size may be collected and processed by ball milling or grinding to meet the requirements of subsequent production processes. More than one sieve or powder dispenser may be employed according to the requirements of the application method to achieve pigment distribution, filtration, or separation.

[0233] Optionally, the system may be adapted to first distribute larger pigments to the article and then apply smaller pigments after the larger pigments are applied. This has particular advantages for pigment fixation because the larger pigments can be used to form a base layer with the article, and the adhesion or fixation of the larger pigments to the article can be achieved through the plasma coating. The subsequently applied smaller pigments can be fixed through another plasma polymerization coating or at least partially embedded in the first plasma polymerization coating. This allows for more complete embedding of the largest-sized pigments, and as the pigment coating or binder grows, the addition of the smaller pigments can make the upper surface of the formed coating relatively flatter.

[0234] Sprinkling pigments onto the article can also achieve pigment distribution in a dry process, which makes it easier to collect the unused pigments at the suction position.

[0235] Another method of particle distribution may include a spray nozzle. The spray nozzle may convey or eject a chemical agent from an outlet through a fluid supply. The spray nozzle may be a hydraulic nozzle with a pressure range of 0.8 - 1.4 bar, a pulse width modulation (PWM) nozzle, or an atomizer with a pressure range of 0.8 - 1.2 bar for a dispersion medium in which particles are dispersed, suspended, or dissolved in a solution. In other examples, the pressure range of the PWM or atomizing nozzle may be from 0.2 bar to 3 bar. The outlet of the spray nozzle may be used to quantitatively or controllably release a fluid to the article 1. In some embodiments, the fluid may be a dispersion containing at least one pigment. The dispersion may be atomized, evaporated, or vaporized, and may carry the pigment in droplets and be ejected from the nozzle. For an aerosol, pigments of a predetermined particle size based on the aerosol droplet size may be used to apply only pigments of a predetermined size or smaller because larger pigments cannot be carried by aerosol droplets below a certain size. By adjusting the aerosol droplet size, this can serve as a screening or pigment filtration method. This can be achieved, for example, by changing the temperature, pressure, or geometric parameters during the atomization process. Other aerosol droplet control methods known in the art may also be employed for atomization.

[0236] The axial velocity range of the liquid ejected by the spray nozzle can be from 15 m / s to about 160 m / s, at which time the liquid pressure is about 1 atmosphere, and the liquid temperature range is from 15 °C to 30 °C. In some embodiments, the liquid ejection speed of the spray nozzle can be higher than 160 m / s, but this is more applicable to thicker articles to be dyed or articles with the function of repelling the liquid from the spray nozzle. The pigment leaving the spray nozzle can also be increased or decreased by changing the speed. In some embodiments, increasing the liquid flow rate can reduce the pigment output. The liquid speed may vary during the spraying process, but the higher the flow rate during spraying, the greater the expected penetration depth into the porous article or textile. If coloring on the extra side of the article surface is required, deeper penetration can provide assistance. In addition, single-sided liquid spraying can achieve the application of a single pigment or colorant to one side of the article 1.

[0237] In another embodiment, the spray applicators within the system can be of the same type or a mixture of one or more types to achieve the desired pigment or dispersion application effect. Air atomizing nozzles or hydraulic atomizing nozzles can be used to apply the pigment. The pigment can be contained in a dispersion, applied in the form of a gel, or applied as a dry or relatively dry pigment. An adhesive can be used to temporarily bond, fix, or adsorb the pigment to the surface of the article 1. It should be noted that in some embodiments, the use of dry pigment can also be referred to as fluid application in this article, but the fluid can be a dry fluid.

[0238] The pulse width modulation nozzle can adjust the fluid output, thereby changing the intensity of the applied color. The color intensity can be adjusted in any desired manner so that uniform coloring of the article 1 can be achieved, or pulsed, wavy, gradient, or other desired special effects can be produced on the article. The applied effect can be an optical effect or a pattern effect. The system can control the output volume of the dispersion or solution, thereby increasing or decreasing the volume provided to the article 1.

[0239] The spray nozzle can spray the pigment-containing dispersion or solution onto the article at a predetermined distance and / or a predetermined speed. The nozzle pressure or spray speed can determine the level of penetration depth into the article, such as a porous article. The penetration depth is particularly important for the application of colorants to textiles, fabric substrates, or non-fabric substrates. The penetration depth is at least 20% of the article thickness. It should be understood that the penetration depth can also be limited to 50% or less in order to apply a first colorant to the first side of the article 1 while applying a second colorant to the second side of the article 1. Alternatively, the penetration depth of the colorant can be predetermined to impart an expected effect to the article and can be selectively applied to one or more sides of the article 1. For example, a dispersion containing a colored pigment can be applied to the article 1 to a depth of 50% of the article thickness, and a second dispersion can be applied to a shallower or deeper depth to achieve an expected color gradient, color change, or color effects such as pearlescent, shiny, or glossy.

[0240] The spray coater can be a removable cartridge within the system 10 for maintenance or cleaning. The cartridge spray coater can also be loaded with the desired dispersions, slurries, colorants, or other materials to be sprayed onto the article 1.

[0241] The particles can be distributed in a solvent or solution, such as ethanol or water, or a chemical agent can be used as an adhesive or part of an adhesive that can react with another chemical agent provided in the plasma polymerization stage.

[0242] The solvent-based ink can be dispersed and coated onto the article by the system, which can include pigments carried by alcohols and / or oils. In some configurations, the pigments can also be carried by water, such as water-based ink, or other liquids suitable for dispersing the ink. The solvent-based ink and the water-based ink can be evaporated and the colorant remains on the article 1.

[0243] If the system is configured to apply pigments to the article 1 using a dispersion or other liquid, the system can also include a drying section with a heater. The drying section can be located between the spray coater and the plasma module so that the article can be dried or at least partially dried of the dispersion, solvent, or other liquid before being processed by the plasma module or before applying a plasma coating to fix the pigments in place. The heater of the drying section should be configured to remove the least amount of liquid on the article before it is processed by the module 20 of the system 10. It should be understood that the liquid applied by the pigment applicator is preferably removed before contacting the plasma because the liquid applied by the pigment applicator is preferably not suitable for polymerization in the plasma region.

[0244] Heaters particularly suitable for this system can include ceramic heaters or glass lamp heaters, where radiant heat can be used to evaporate the solvent or other liquid on the surface of the article before plasma treatment or applying a plasma coating. These types of heaters have corrosion-resistant properties and can operate in a plasma gas environment or in a volatile evaporant environment. The heating element can be provided with at least one suction area adjacent to the heater for removing moisture or evaporative materials from the system 10. The suction area can promote the movement of the evaporating liquid through a pressure difference or actively entrain the fluid to remove it from the interior of the system. Optionally, the fluid collected from the suction device can pass through a recirculation system, where a cold trap or other liquid removal system can be used to condense and separate the evaporative fluid captured by the suction.

[0245] The heaters installed in the system can be selectively configured with a heater shroud, which can isolate other components of the system 10. In addition, the heater shroud can be built with a suction area so that the shroud surrounds both the heater and the suctioned evaporating liquid. There is a gap below the shroud for the article to pass through, and its size is designed to prevent the evaporating liquid from entering the chamber area adjacent to the heater shroud to the greatest extent.

[0246] After the article passes under the heater shroud, the article can be cooled by the plasma gas in the chamber and reach the desired temperature before entering the plasma region. This is beneficial for certain types of coatings because the temperature of the article needs to be controlled within the range of -10°C to 40°C when implementing plasma coatings.

[0247] In another embodiment, the system 10 can employ a padding device to apply pigments in a solution / solvent to the article 1. The padding device is provided with feed rollers and one or more mercerizing rollers. The first two mercerizing rollers that form the inlet roller pair are designed as pneumatic squeegees, and their gaps are substantially at the position of the mercerizing liquid level. In this way, when the article, especially a tubular object, enters the liquid from the air, air can be effectively removed from the article, thereby improving the treatment effect of the liquid on the article. The last mercerizing roller leans against the adjacent dyeing padding roller, and each mercerizing roller is at least partially intermittently immersed in the treatment liquid in the mercerizing container. The dyeing padding roller is designed as a driving roller, and a squeezing roller is provided above it. The squeezing roller can be lifted from the driving roller, is supported by means of rotation such as a pivoting arm, and the lifting movement from the driving roller can be implemented through a lifting mechanism such as an adjusting pneumatic cylinder. In addition, spray nozzles are installed at a position approximately flush with the squeezing roller. When the article starts to wind back in the intermittent operation mode, the article can be pre-cleaned through these nozzles. A cooling tank and a pumping device are also provided below the mercerizing container to implement the aforementioned intermittent mercerizing treatment process.

[0248] Optionally, the pigment, which can be a colorant, can be applied to the article in the form of foam. The foam can be formed from a dispersion of the pigment in a liquid or other medium. The foam expands through an injection nozzle and covers at least a part of the article to be treated. The foam can also evenly distribute the pigment inside it before it shrinks, thereby transporting the pigment on the article 1. By restricting the chamber space leading to the air lock or the roller, the foam applied to the article can be guided to flow in the required direction. This can form a desired or uniform foam thickness on the article before plasma treatment.

[0249] In another embodiment, the system can be configured to apply pigments or powders to a substrate. The pigments applied to the substrate can be implemented by at least one of the following methods: electrostatic powder spraying (or pigment spraying) method, drum transfer method, powder sprinkling method, nozzle spraying method, padding method, foam application method, anilox roll coating method, and printing method. Other methods can also be applicable and can be described herein.

[0250] The particle size range of the pigments and powders applicable to the present disclosure is from 1 nanometer to 900 micrometers. Preferably, the thickness range of the pigments or powders used is from 10 nanometers to 1000 nanometers, or from 200 nanometers to 1000 nanometers, or from 400 nanometers to 600 nanometers, or in some cases, the average particle size can be from 1 nanometer to 200 nanometers. It should be noted that the pigment size may refer only to the material size in a single plane, and the pigments, powders, and particles may have a flaky geometric shape or other geometric shapes required for specific applications.

[0251] For example, mica particles or pigments with a thickness of 1 - 10 nanometers can be used, and their width dimension is at least one order of magnitude larger than the thickness. When the flaky pigments or particles are applied to the substrate, they can be randomly oriented, or their orientation can be controlled to be relatively more parallel to the substrate surface.

[0252] The color selection method can be similar to the traditional printing method using monochromatic to six - color methods, or in some embodiments, a seven - color method can be used. Pigments, dyes, or other colorants can be used in the method to provide each color spectrum. The colorants can be applied through one or more application processes, and a dedicated pigment applicator can be configured to provide a specific color, or one or more pigment applicators can be used to apply one or more colorants as needed.

[0253] In another embodiment, the color - developing pigments can be applied to the article in an array of the CMYK (cyan, magenta, yellow, black) color system. The CMYK coloring of the article can be achieved using halftone or screening techniques, which allow the primary colors to be presented in a non - fully saturated state. This method forms the desired visual coloring effect by printing fine dots of each primary color in a predetermined manner.

[0254] The system 10 can be configured to allow for the pre - mixing of coloring pigments to form the desired colorant to be applied to the article 1. In another embodiment, a progressive pigment application method can be employed, where a first pigment application module is used to apply a fixed pigment or pigment mixture to the article 1, and subsequently a second pigment applicator is used to apply a second pigment or pigment mixture to the article. In this way, more than two pigment applicators can be used, with each applicator configured to apply one or more predetermined pigments to the article. In this manner, an expected pigment with an expected color is formed by the application of multiple pigment colorants. In a further embodiment, a pigment applicator corresponding to one of the colorants in each of the CMYK processes can be provided, such that four pigment applicators can be used in the process. Similarly, any number of pigment applicators can be configured in the system, with each applicator corresponding to a specific colorant of a color process from a single - color process to a seven - color process. In addition to the number of applicators required for a predetermined color process, the system 10 can also include a white pigment applicator in addition to other pigment applicators. That is, in a seven - color configuration, approximately eight pigment applicators 18 need to be provided. More than one pigment applicator can act on the same area of the article at any time, enabling the synchronous application of two or more spray applicators. It should be understood that the pigment applicators can be spray applicators.

[0255] The colorant can be adjusted by controlling the loading rate of the pigment on the article, or by adding a white pigment colorant or a light - tone pigment colorant to increase or change the color intensity or the overall visual effect applied to the article. Each colorant can be applied to the article in a predetermined volume or weight, and the system controller 11 can be configured to apply the correct volume or loading amount to obtain the desired final coloring effect on the article.

[0256] In another method, the system can also employ spot - color printing to generate colors on the article 1 with specific colorants. The spot color or solid color can be an ink, pigment, or other colorant, which can be a pure color or a mixed color, any color formed by a single application to the article; while process colors are achieved by printing or applying a series of different - colored dots to achieve the expected color perceptible to the observer. The dots can be applied to the article 1 as pigments in a printing, spraying, or depositing manner. The CMYKOG method can employ a color - system array similar to CMYK, but additionally includes orange and green colorants, providing a more vivid and precise color representation compared to the CMYK method.

[0257] Optionally, Pantone can be used TMA color system, which is a six-color system CMYKOG, can greatly expand the color gamut range of available colors. However, it should be understood that other six-color methods can also be used, such as the CcMmYK coloring method, which additionally adds light magenta and light cyan colorants. Light saturated colors are usually not achievable by CMYK, and light colors are prone to revealing halftone screens. The CcMmYK process of adding light cyan and light magenta inks to CMYK can solve such problems.

[0258] Although examples of some color systems have been discussed, it should be understood that this system can be adapted to use one or more other standardized or common color systems in the industrial field. For example, the system can be configured to use at least one of the following systems: Pantone TM , Toyo TM , DIC TM standard color cards, ANPA TM , GCMI TM , HKS TM (jointly developed by Hostmann-Steinberg Druckfarben, Kast, Ehinger Druckfarben and H.Schmincke&Co.) and RAL TM .

[0259] RAL CLASSIC TM The RAL CLASSIC color system is mainly applicable to powder coating colorants and can provide the required classification method for multiple industries. It should be understood that since each system is independently designed, the colors of the first coloring system may not be achievable by the second coloring system. However, this system can be adapted to be compatible with pigments or other colorants of more than one coloring system.

[0260] Since some pigments are less needed or some are used less frequently than other pigments, the system can be configured with one or more devices for stirring, mixing, moving or ultrasonic treating the pigments before applying them to the article 1. This can allow the final colorant applied to the article 1 to have higher consistency.

[0261] The pigments can be optically evaluated to obtain their average color values, and the system 10 can be configured to dynamically adjust the final colorant by mixing pigments in a predetermined proportional manner. This mixed pigment colorant can be similar to conventional printing methods.

[0262] Similar to traditional laser printing devices, the pigment applicator can be configured to add colorants in a predetermined manner to form a predetermined color pattern or image. Multiple coloring or developing units can be installed on a rotating shaft or a rotating wheel. In this way, the printer can first apply a monochromatic electrostatic image and then position the toner to the desired location. After the color application is completed, the next required color can be moved to the position to repeat the process.

[0263] Optionally, all colorants can be added to the printing plate before the image is transferred to the article. Depending on the geometry, thickness, or surface topography of the article, certain methods of applying pigments to the article may be restricted.

[0264] Natural pigments can include plant pigments such as chlorophyll, anthocyanins, carotenoids, and betalains. Natural pigments can also include biological pigments selected from the following groups: heme / porphyrin-based pigments, chlorophyll, bilirubin, hemocyanin, hemoglobin, myoglobin, luminescent pigments: luciferin, hematochrome (a mixture of algal pigments, carotenoids and their derivatives, carotene, alpha and beta carotene, lycopene, rhodopsin, xanthophylls, canthaxanthin, zeaxanthin, lutein, proteinaceous pigments, phytochrome, phycobiliproteins, psittacofulvins, turacin and turacoverdin, melanin, urochrome, and flavonoids. In addition, algal pigments are also suitable for plasma coatings. These pigments include: chlorophyll a, b pigments and chlorophyll c, phycobiliproteins, phycoerythrin, lutein, and fucoxanthin pigments. Biosynthetic dyes can also be used to generate the required colorants or pigments through bacteria, sugars, or other organic substances.

[0265] Pigments with selected color absorption characteristics can be added to the coating. Such pigments can be synthetic products or derived from plant pigments, floral pigments, and biological structural pigments such as chromatophores. In addition, polymerizable chemical agents, monomers, and precursors can also be obtained from biomass raw materials for preparing thin films or plasma polymerization coatings.

[0266] Bioplastic precursors can be obtained from biomass, including plant oils, corn starch, straw, wood chips, sawdust, recycled food waste, seaweed, etc. Some bioplastic precursors are obtained by directly processing natural biopolymers, including polysaccharides (such as starch, cellulose, chitosan, and alginate) and proteins (such as soy protein, gluten, and gelatin); others are chemically synthesized from sugar derivatives (such as lactic acid) and lipids (oils) from animal and plant sources, or are biologically prepared by sugar / lipid fermentation. Based on the above precursors or other biomass raw materials, materials such as bio-based polyethylene terephthalate, bio-based polyethylene, and degradable bioplastics (such as polylactic acid, polybutylene succinate, or polyhydroxyalkanoates) can be produced. These materials are particularly suitable as monomers, precursors, or raw materials for plasma polymerization coatings.

[0267] Polysaccharide-based bioplastics are suitable for being applied to articles through this system. Such bioplastics include: starch-based plastics, cellulose-based plastics, chitosan, and alginate. Chitosan has special advantages because it is easy to integrate pigments and other biopolymers into the polymers formed by it and can be widely used in packaging applications.

[0268] The properties of starch-based bioplastics depend on their amylose / amylopectin ratio. In terms of mechanical properties, a relatively higher amylose ratio in the pigment compared to amylopectin is more favorable. This mechanical property ratio relationship is well-known technology in the field of bioplastic manufacturing and is cited here. Starch-based bioplastics can optionally be mixed or blended with biodegradable polyesters to form starch / polylactic acid, starch / polycaprolactone, or starch / polybutylene adipate-co-terephthalate (commonly known as Ecoflex TM ). Although the above-mentioned starch-based plastics can all be prepared by this system, the system has special advantages in preparing starch-based films suitable for food packaging, wrapping materials, packaging paper, and compostable products. Such films can be formed from pigments containing starch and thermoplastic polymers.

[0269] Another type of plastic that can be formed during plasma polymerization is protein-based plastics. These plastics can be made from gluten, casein, and soy matrices. Aliphatic biodegradable polyesters are mainly polyhydroxyalkanoates (PHAs), such as poly-3-hydroxybutyrate (PHB), polyhydroxyvalerate (PHV), and polyhydroxyhexanoate (PHH). In addition, polylactic acid (PLA) can be easily made into pigments, powders, and granules. Using PLA bioplastics can form, for example, films, fibers, and packaging materials. Polyhydroxyalkanoates are linear polyesters naturally produced by bacterial fermentation of sugars or lipids. Polyhydroxyalkanoate monomers are easily formed into products suitable for medical use. Polyamide 11, polyhydroxyurethane, lipid-derived polymers, and other biobased monomers and / or bioprecursors can all be used in this system and can be provided in liquid or pigment form depending on the application method.

[0270] Bio-based polyethylene can be prepared from ethylene monomers derived from ethanol. Other alcohols are suitable for forming polymers under plasma action. This property has special advantages when it is necessary to carry the pigment in the form of an aerosol or vapor, as the liquid component of the aerosol or vapor can be ethanol or ethylene monomer.

[0271] Pigments can generally be classified into the following categories: white pigments, colored pigments, black pigments, and special pigments. These pigments can be sourced from natural sources, synthetic sources, or a combination of both. Particles that are insoluble in the coating medium (varnishes, synthetic materials, printing inks, cosmetic formulations, and building materials) can also be used as components of the coating.

[0272] White pigments impart color to the product by diffuse reflection of light. Absorptive pigments develop color through light absorption (and additional diffuse reflection). Pigments containing metals produce luster through light reflection and can be metallic pigments. Special effect pigments, such as pearlescent pigments, present color, luster, and / or interference effects through light reflection and refraction (interference effects). The above pigment properties can also be further enhanced by plasma coatings above and below them to achieve the desired effects.

[0273] Special pigments may include transparent pigments, functional pigments, and effect pigments. Effect pigments can be further subdivided into two subcategories: metallic effect pigments and special effect pigments. Metallic effect pigments preferably contain aluminum and / or copper-zinc alloys, while special effect pigments include pearlescent pigments and interference pigments.

[0274] Although the pigments described herein may be referred to as having a substantially uniform diameter or size, it should be understood that this is a simplified representation, and the actual pigment surface is usually irregular or wavy due to the preparation method. The pigment particle size range applicable to the methods and systems of this application is from 0.1 μm to 200 μm. However, the size of effect pigments can be larger than that of simple coloring pigments. The particle size of effect pigments can be from 5 μm to 100 μm, and these pigments have the additional characteristic of transparent, translucent, or opaque flaky particles. Other effects imparted by the pigments also include one or more functional properties, such as: magnetic, anti-corrosion, luminescent, antibacterial, antiviral, flame-retardant, hydrophobic, hydrophilic, self-cleaning, and oleophobic properties.

[0275] Effect pigments are generally divided into two categories: metallic effect pigments and special effect pigments. Both metallic effect pigments and special effect pigments produce a gloss effect on the colored surface through the reflection of light on the pigments. In special effect pigments, the pearlescent effect and the interference effect are caused by the separation of incident light on the pigment surface. Since only part of the light is reflected, while the other part of the light penetrates the transparent or translucent particles and reaches the deep interface layer and is then reflected. This results in the superposition of light waves, producing an enhancement or weakening effect according to their wavelengths, that is, forming an interference phenomenon.

[0276] By selecting metal oxide pigments that match the refractive index of the binder (plasma polymerization coating) and controlling the thickness of the plasma polymerization coating, various effects combining color interference phenomena and gloss effects can be produced. The thickness of these coatings is preferably from 5 nm to 500 nm. By changing the pigment particle size, various effects can be achieved, from velvet matte to high-gloss transparent and even semi-matte. The application of such pigments can use a sieve-type pigment application method, where the pigment particle size can be controlled, or a combination of multi-layer pigment application and plasma polymerization coating can be used to achieve the desired effect.

[0277] Pigment selection can be based on the refractive index of the pigment and the thickness of the plasma polymerization coating and / or the opacity of the plasma polymerization coating. By evaluating these characteristics, bright interference colors or interference pigments can be applied to the article. In contrast, metallic luster is only produced by the simple reflection of light by metal platelets. The interaction of visible light is the basis of special effect pigments and metallic effect pigments.

[0278] Any predetermined pigment can be used in the plasma polymerization coating. The plasma polymerization coating can contain at least one colorant or functional pigment.

[0279] In another embodiment, pigments can be provided during or prior to polymerization to facilitate coating formation and deposition rate. Since the polymerization chemicals are more likely to be captured on the surface of the article, the pigments on the surface can improve the coating thickness and / or coating adhesion. This property has particular advantages when the chemicals, monomers or precursors are provided to the article through a plasma region.

[0280] In another embodiment, the pigment particle size can range from 10 nanometers to 1000 nanometers, but more precise particle size ranges can be preferred depending on the optical effects of the pigments within the desired range. For example, certain pigment particle sizes are preferably 300 - 450 nanometers to achieve the desired gloss, opacity, transparency or coating embedding properties.

[0281] A variety of natural pigments suitable for dyeing purposes can be subjected to plasma coating or plasma treatment steps. These pigments can be embedded in the coatings applied by the plasma polymerization step or within the coatings polymerized by the post - plasma polymerization step. Natural pigments can be extracted from natural sources, which include but are not limited to: plant roots, nuts, fruits, vegetables and flowers. Carbon - based pigments captured from industrial emissions or other carbon dioxide emission sources can also be used.

[0282] Other pigments can be derived from recycled materials, including recycled clothing pigments, recycled plastics, recycled packaging and recycled glass. Pigments extracted from other recycling applications can also be used.

[0283] In another embodiment, mica can be used as the pigment contained in the coating. Mica is generally a natural mineral and can impart a specific luster to the color. In addition, mica pigments can be provided in any predetermined size or desired color, and their appearance is usually planar or flaky. The surface size of mica pigments ranges from 10 microns to 100 microns, and the thickness ranges from 200 nanometers to 10 microns.

[0284] Mica pigments are preferably used because the thickness range of the plasma coating can be from 100 nanometers to 500 microns, depending on the processing time and parameters. Therefore, the thickness of mica enables it to be arranged relatively parallel to the surface of the article to be coated and be substantially wrapped or mostly embedded in the plasma polymerization coating.

[0285] Mica pigments are usually selected based on opacity, transparency, and / or gloss. For reference: mica particles with a particle size ≤ 15 μm have low gloss and high opacity, particle sizes of 2 - 25 μm exhibit a silky effect and relatively high opacity, particle sizes of 10 - 60 μm have a pearlescent gloss and medium to medium opacity, particle sizes of 10 - 125 μm exhibit a shimmering gloss and a lower opacity tending towards transparency, particle sizes of 20 - 150 μm are usually transparent and have a glittering gloss, and particle sizes of 45 - 500 μm exhibit a shimmering gloss with higher transparency and can be very transparent. The plasma coating used to fix these pigments also affects the gloss or opacity / transparency of the pigments. For example, a plasma coating can be used to reduce the gloss of naturally or inherently high - gloss pigments, giving the pigments a more matte appearance. Some pigments, after being embedded, encapsulated, or combined with a plasma coating, can also confer additional functionality.

[0286] Other metals and inorganic materials that can be used as pigments can be selected from the following groups: titanium, aluminum, zinc, gold, cesium, copper; sulfates of calcium, strontium, and barium; zinc sulfide; copper sulfide; titanium dioxide and barium zeolite; mica; talc; kaolin; mullite or silica. Additionally, lead or mercury compounds can also be used according to application requirements. The average diameter of the deposited metal can be from 0.01 to 200 microns, preferably 5 to 100 microns.

[0287] The textile receiving the metal coating can be an inorganic particle having a first coating of a metal or metal compound and a second coating of silica, silicate, borosilicate, aluminosilicate, alumina, or a mixture thereof.

[0288] The inorganic particle, i.e., the core material, can be oxides of titanium, aluminum, zinc, copper, calcium, strontium, barium, and lead. Optionally, the material can also be a sulfide or sulfate. It is preferred to use nearly pure metals or metal alloys to form the pigments for the pathogen - interfering layer. However, it should be understood that other compounds, such as silver nitrate (AgNO3) or titanium dioxide (TiO2), can also be used. Other pigments commonly used in the industry, including organic and inorganic pigments, can also be used as needed.

[0289] In one embodiment, the pigment can form at least a partially continuous coating or film that can conform to the surface topography of the substrate 10. After deposition, a protective layer, covering layer, or functional coating can be applied to the pigment to reduce the risk of the pigment detaching from the substrate 10. The characteristics of the functional coating can include at least one of the following: flame - retardant, ultraviolet - absorbing, self - cleaning, hydrophobic, hydrophilic, and / or antibacterial. Other functionalization treatments known in the art can also be applied.

[0290] In other embodiments, the pigments may be suitably formulated in a suitable carrier, coating, or solvent such as water, methanol, ethanol, acetone, water-soluble polymer binders such as polyvinyl acetate (PVA), epoxy resins, polyesters, etc., as well as coupling agents, antistatic agents. A biological material solution such as phosphate buffered saline (PBS) or simulated body fluid (SBF) may also be used. The concentration range of the pigments in the solution may be from 0.001% (by weight) to about 20% (by weight). Subsequently, these pigments may form a coating that can be applied to the substrate 10.

[0291] Flame retardants reduce or inhibit the flammability of textiles through the following mechanisms: reducing heat generation during combustion, reducing flammable volatiles, altering pyrolysis reactions, forming an expanded carbon layer, releasing moisture, releasing gaseous flame retardants such as chlorides and phosphorus compounds.

[0292] Particles suitable for flame retardant coatings may include particles selected from the group consisting of: nanoclays, zinc borate, carbon nanotubes (CNT), layered double hydroxides (LDH), polyhedral oligomeric silsesquioxanes (POSS), silica (SiO2), and metallic pigments. Optionally, the SiO2 may be of nanoscale dimensions. Any combination of particles may be used in a single coating. Optionally, the coating may be formed by multi-layer lamination.

[0293] Suitable nanoclays may be layered silicate mineral pigments, which can be classified into multiple categories according to chemical composition and morphology, such as montmorillonite (MMT) and halloysite. Metallic pigments may also be metal-based pigments or oxides such as titanium dioxide (TiO2), zinc oxide (ZnO), aluminum oxide (Al2O3), etc.

[0294] Preferably, the thickness of the applied coating is at least 100 nanometers. More preferably, the thickness range of the flame retardant treatment or coating is from 100 nanometers to 100 micrometers.

[0295] Preferably, the char yield of the substrate can be increased by applying a flame retardant coating. The coating preferably contains particles, such as fine particles or nanoparticles. After coating treatment, the char yield test should be increased by at least 1% compared to the substrate without such treatment.

[0296] The thickness range of the coating may be from 50 nanometers to 900 micrometers. More preferably, the thickness range of the coating is from 150 nanometers to 900 nanometers. Preferably, the ratio range of the coating thickness to the particle diameter is from 1:1 to 1:500, more preferably from 1:2 to 1:200. It should be understood that the average thickness of the coating may be determined relative to the diameter of the particles within the coating.

[0297] Preferably, the particle diameter or size in the coating is substantially uniform. It should be understood that a distribution of particle sizes can be provided in the coating, where the distribution includes particle sizes within a known size range, and the remaining particles are larger or smaller than the known size range. For example, 80% by volume of the particles in the coating are within the known particle size range, and the remaining 20% by volume of the particles have a particle size smaller or larger than the known particle size range. In another embodiment, 80% by weight of the particles in the coating are within the known particle size range, and the remaining 20% by weight of the particles have a particle size smaller or larger than the particle size range.

[0298] Optionally, the applied particle coating can form a flame retardant coating or can be used in combination with a flame retardant coating applied by chemical vapor deposition process. Preferably, any such deposition process is a plasma enhanced chemical vapor deposition process.

[0299] The particles for the flame retardant coating can be applied by coating laminates or can be uniformly distributed throughout the coating. The particles can be deposited on the surface of the substrate to be coated with the functional coating or can be applied to the substrate synchronously with the functional coating.

[0300] Preferably, the coating thickness or the amount of coating accumulated at the particle contact end is sufficient to embed the particles or fix the particles in the desired position. The coating thickness can cover at least 5% of the particle height. Preferably, the particles are coated.

[0301] Optionally, a precursor capable of generating functional properties can be used in combination with the pigment selection or as a functional binder for the pigment, thereby avoiding other post-treatment functional chemical processes or restricting their use to reduce downstream resource consumption.

[0302] The system 10 can deposit a variety of polymer coatings, polymer films, pigment coatings, and pigment treatment layers on the article 1. Non-limiting examples of coating monomers include at least one monomer selected from the following group: acetylene, ethylene, isoprene, hexamethyldisiloxane (HMDSO), tetraethoxysilane (TEOS), tetraethyloxysilane, orange oil, tea tree oil, peppermint oil, ethanol, butanol, lactic acid, ethyl acetate, γ-valerolactone, cyclopentene (dihydrolevoglucose ketone), ε-caprolactam, ethyl lactate, stearic acid, candelilla, carnauba wax yellow 1, beeswax, diethyldimethylsiloxane, 1,3-butadiene, styrene, methylstyrene, tetrafluoroethylene (TFE), methane, ethane, propane, butane, pentane, hexane, cyclohexane, acetylene, ethylene, propylene, benzene, isoprene, hexamethyldisiloxane, tetraethoxysilane, tetraethyloxysilane, diethyldimethylsiloxane, 1,3-butadiene, styrene, methyl Methyl acrylate, tetrafluoroethylene, pyrrole, cyclohexane, 1-hexene, allylamine, acetylacetone, ethylene oxide, glycidyl methacrylate, acetonitrile, tetrahydrofuran, ethyl acetate, acetic anhydride, aminopropyl triethyleneoxyethane, triethoxyethoxytetraethoxyethyl, triethoxyethoxyethyl ester, triethoxyethyl triethylethoxyethanol, triethoxyethoxyethyl ether, triethoxyethanol, triethylthioethoxyethyl, triethoxyethyl, trimethoxyethyl, triethoxyethoxyethyl, triethoxytriethoxyethane, ethoxytrimethoxyethyl, triethoxyethyl, triethanol, ethoxydiethoxydiethyl iron, tricarbonyl (cyclooctatetraene) iron, dicarbonyl (methylcyclopentadienyl) iron, cyclopentadienyl cobalt, cobalt acetylacetonate, nickel acetylacetonate, di(2,4-pentanedioate)gold(III), carbonyl nickel, carbonyl iron, tin acetylacetonate, indium acetylacetonate, indium tetramethylheptanedioate.

[0303] Preferably, the article is free of moisture prior to plasma treatment or plasma coating. Alternatively, the colorant may be dispersed into the article using an oil which may polymerize to fix the colorant to the article.

[0304] The oils that can be used are preferably bio-based oils, but synthetic oils can also be used as needed. The bio-based oil can be an essential oil, for example an oil selected from the following group: coconut oil, olive oil, sunflower oil, shea butter, jojoba oil, almond oil, grape seed oil, rose hip seed oil, orange oil, allspice oil, coriander seed anhydrous almond oil, angelica root oil, fennel oil, star anise, star oil, ginseng oil, Atlas cedar oil, balsam fir oil, balsamic vinegar, Peruvian oil, basil oil, basil, holy oil, bay leaf oil, laurel oil, beeswax absolute benzoin absolute bergamot oil, bergamot mint oil, black pepper oil, black spruce oil, blood orange oil, blue cypress oil, blue tansy oil, rose oil, boric acid an absolute bergamot oil, cardamom oil, cardamom oil. Jept oil, camphor, white oil, cananga oil, hemp oil, caraway oil, cardamom oil, carrot seed oil, cassia oil, catnip oil, cedar, atlas oil, cedarwood, virginia oil, chamomile, german oil, chamomile, roman oil, chocolate mint oil, coriander oil, cinnamon oil, brain pool oil, citronella oil, twig sage oil, clove oil, coffee oil, common sage oil, copal balsam oil, coriander oil, corn mint oil, cubeb oil, cumin oil, cypress oil, cypress, blue oil, cypress, japanese oil, cypress, taiwanese oil, davana oil, dill oil, dalmatian sage oil, douglas fir oil, elemi Fatty oil, eucalyptus oil, eucalyptus, lemon oil, radiata eucalyptus oil, anise oil, fir, balsam oil, fir, Douglas oil, fir, Siberian oil, fir oil, silver oil, fragrant tea tree essential oil, frankincense oil, galbanum oil, geranium oil, geranium oil, rose oil, German chamomile oil, green moss oil, ginger oil, one-flower oil, grapefruit oil, balsam, melaleuca oil, melaleuca oil cycad oil, hemlock spruce oil, hemp oil, wild wood oil, wild wood oil, Taiwan oil, lotus leaf oil, lotus oil, holy basil oil, red cinnamon oil, hops oil, hyssop oil, Shiping oil, emote oil, Japanese cypress oil, jasmine absolute jasmine oil, claw Peppercorn Oil, Juniper Oil, Bright Oil, Kunzea Oil, Cistus Oil, Lemon Oil, Bay Leaf Oil, Lavender Oil, Lavender, Lancet Oil, Lemon Oil, Lemon Wind Oil Essential Oil, Lemon Eucalyptus Oil, Lemongrass Oil, Lemon Myrtle Oil, Lemon Tea Tree Oil, Lemon Verbena Oil, Lime Oil, Linden Flower Absolute Citrus Oil, Manuka Oil, Marjoram Oil, Plum Oil, Melissa Oil, Myrrh Oil, Myrrh, Sweet Oil, Myrtle Oil, Myrtle, Lemon Oil, Spikenard Oil, Neroli Oil, Guano Oil, Nutmeg Oil, Oakmoss Absolute Cocoa Butter, Frankincense Oil, Myrrh Oil, Orange, Bitter Oil, Orange Oil, Blood Oil, Orange Essential Oil, Sweet Oil,Origanum oil, Rosa palmate oil, Croton oil, Parsley oil, Patchouli oil, Pepper, Black oil, Pepper oil, Peppermint oil, Peppermint, Chocolate oil, Balsam Peru oil, Small grain oil, Sweet pepper berry / leaf oil, Pine tree, Pine nut oil, Pinewood, Scotch oil, Pink pepper oil, Lattice oil, Red pine oil, Ravensara oil, Ravintsara oil, Cistus oil, Rhododendron oil, Roman chamomile oil, Rose oil, Rose essential oil, Rose essential oil and Rose CO2 extract Rosemary oil, Rosewood oil, Sage, Ash oil, Buckthorn oil, Common oil, Rat sage, Dalmatian oil, Rat beard, Spanish oil, Rat leek, White oil, Sandalwood oil, Shorea oil, Scotch pine oil, Siberian fir oil, Silver fir oil, Spearmint oil, Spike lavender oil, Spike essential oil, Spruce, Hemlock oil, Spruce, Black oil, Star anise oil, Sweet myrrh oil, Sweet orange oil, Citronella oil, Tangerine oil, Tan, Blue oil, Taiwan camphor oil, Tea tree oil, Common oil, Tea tree, Lemon oil, Tea tree, New Zealand oil, Thyme oil, Tobacco absolute Tuberose absolute Dulci oil, Valerian oil, Vanilla absolute and Vanilla co2 extract Verbena, Lemon oil Ylang-ylang oil, Grapefruit oil, Ethanol, Butanol, Lactic acid, Ethyl acetate, γ-Valerolactone, Butene (dihydrolevoglucosenone), ε-Caprolactam, Ethyl lactate, Stearic acid, Euphorbia cerifera, Carnauba wax No. 1 yellow, Beeswax. Other essential oils or bio-derived precursors / monomers may also be used as needed.,

[0305] Preferably, any bio-based oil should have a double bond structure or volatile properties for evaporation and / or vaporization. After evaporation, atomization or vaporization of chemical agents including bio-based oils, they can be introduced into the plasma region generated by the plasma module 20 for polymerization. However, if the system is configured to coat oils through a pigment applicator, the oil preferably contains double bonds in its molecular structure that can participate in the polymerization reaction.,

[0306] In at least one embodiment, organic and / or inorganic coatings can be applied. Inorganic coating precursors include pure metals, metal salts, oxides, nitrides, carbides or combinations thereof. In another embodiment, the system 10 can coat various particles sized from nanometers to micrometers. The coating can be deposited through gaseous, liquid or solid precursors, but is preferably implemented in a vaporized or aerosol state.,

[0307] In addition, pigments with a particle size of about 10 nm to 100 nm can be used as components of a larger molecular structure, which is typically about 100 nm to 1,000 nm. For example, the pigment size can be increased by surface coating, embedding it in a suitable carrier, or compounding it with other particles / materials to form larger particles. In certain embodiments, if at least one size of at least one pigment in the pigment solution is less than 50 nm to 100 nm, the surface of the pigment can be coated with a non-conductive matrix of 10 nm to 100 nm or thicker to increase the size or particle to 50 nm to 100 nm or larger. This increased size can improve the deposition supply of the pigment on the article 1.,

[0308] In another embodiment, the pigment has optical absorption characteristics of from about 10 nm to about 10,000 nm, such as 100 nm - 500 nm. Optionally, the optical absorption characteristics of the pigment are suitable for excitation by a standard laser device or other light source. For example, the pigment can be adapted to absorb wavelengths of about 755 nm, about 800 nm to 810 nm, or about 1,000 nm to 1,100 nm. Similarly, the pigment can also be adapted to absorb intense pulsed light in the range of about 500 nm to 1,200 nm.

[0309] The pigments provided herein generally comprise a non-assembled pigment collection. The term "non-assembled" means that the pigments in the collection are not directly (particle - molecular formula) or indirectly (e.g., particle - cellular component - protein component - analyte component) connected to each other by physical forces or chemical bonds. In other embodiments, the pigment composition can be assembled into an ordered matrix. In particular, the ordered matrix includes any three-dimensional matrix. In certain embodiments, only a portion of the pigments, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 86%, 90%, 95%, 99% or more, are assembled in an ordered array. The pigments are assembled through van der Waals forces, London forces, hydrogen bonds, dipole-dipole interactions, covalent bonds, or combinations thereof.

[0310] The average particle size of the microparticles and the pigment is from about 10 nm to 10 μm, and they are distributed on the polymer surface at intervals of 10 nm to 3000 nm, and their arrangement structure is formed according to the size of the applied particles.

[0311] The plasma polymerized coating formed by module 20 on the article can be a protective coating for retarding the diffusion of internal pigment ions, or a functional layer providing at least one functional property selected from the following group: flame retardancy, ultraviolet absorption, self-cleaning, hydrophobicity, hydrophilicity, and / or antibacterial property. Other functional treatments known in the art can also be used.

[0312] The pigment or the plasma polymerized coating can be used to provide at least one of hydrophobic and / or hydrophilic functions. A hydrophobic and / or hydrophilic coating can be formed on article 1 using a siloxane chemical formulation. The functional properties of such coatings depend on the coating thickness, the porosity of the article being treated, and the properties of the applied pigment (if any).

[0313] The hydrophilic pigment generally can comprise a transition metal or its oxide or complex. These pigments described herein can be incorporated into the plasma polymerized coating and are generally applied simultaneously with the plasma coating, or as part of an on-line process.

[0314] Some examples of hydrophobic pigments can include: manganese oxide polystyrene (MnO2 / PS), zinc oxide polystyrene (ZnO / PS) nanocomposites, precipitated calcium carbonate, carbon nanotube structures, silica nanocoatings, and siloxane particles. Fluorosilanes, fluoropolymer coatings, and siloxane coatings can be used as binders for the pigments while providing hydrophobic functionality.

[0315] Hydrophilic pigments can be applied in a solvent, which includes: ketones such as acetone or methyl ethyl ketone, alkanols such as ethanol or ethylene glycol, ethers such as diethyl ether, esters such as ethyl acetate, and acetonitrile. After plasma treatment, the solvent can form a partial plasma polymerized coating on the article, and can also be removed from the article by volatilization or substantially removed before applying the plasma polymerized coating to the article.

[0316] The hydrophobic property or superhydrophobic property can be provided solely by the plasma polymerized coating, solely by the pigment, or by both. Similarly, a hydrophilic coating can be achieved in a similar manner.

[0317] The use of at least one of the pigments and / or the plasma polymerized coating can also impart a soft touch. Soft touch is generally used as a measure for textiles or clothing, where the feel of the treated substrate or textile is substantially unchanged or further softened compared to the untreated substrate or textile. A softer feel can also be related to the drapability of the substrate or textile. The main advantage of forming a plasma polymerized coating on a substrate using plasma polymerization technology is that it can impart functionality while improving the feel. This property is particularly significant in plasma coatings applied to a substrate after a plasma region generated by chemical agents, monomers, or precursors through module 20.

[0318] Alternatively, a thinner coating can be applied through a sprayer, vaporizer, or nebulizer and then polymerized through a plasma region. However, the difficulty with this application method is that it may cause agglomeration or consolidation of the applied fluid, resulting in an uneven coating if under non-optimal conditions or if the interval between application and plasma treatment is too long.

[0319] Preferably, during the plasma exposure step, or when chemical agents, monomers, or precursors pass through a plasma region before being applied to the article, the plasma polymerized coating is applied to the article. This is because this method can more precisely control the coating thickness compared to conventional coating methods such as dipping, scraping, or spraying. Chemical agents, monomers, or precursors preferably entering the plasma region in a droplet, vapor, or atomized state can be fully dissociated and polymerized on the substrate to form a highly cross-linked structure and then deposited on the article, thus enabling the growth of the coating or film as required. This growth mode of the coating or film can reduce the total material consumption required to form a functional coating on article 1.

[0320] Pigments of CuO, TiO2, and / or AgNO3 with self-cleaning or deodorizing functions can be applied to article 1, where copper or silver ions can diffuse to the surface of the plasma polymerized coating that encapsulates the pigments, creating an environment unfavorable for the survival of bacteria, microorganisms, viruses, or other biological substances. Alternatively, the self-cleaning coating can serve as the main coating applied to article 1. When exposed to sunlight, these coatings can react with water to generate hydroxyl radicals. These radicals can decompose organic molecules and microorganisms adsorbed on the coating surface. When a fluid, such as water, is applied to the coating, the liquid can be absorbed and carry away or substantially remove surface dust, dirt, grease, and other contaminants. Other self-cleaning coatings with different activation or cleaning reaction mechanisms can also be applied. However, it should be understood that system 10 is capable of applying any self-cleaning coating.

[0321] The self-cleaning coating can be applied to clothing, medical devices, high-frequency contact items, vehicles, airplanes, and public facilities. The coating can be applied multiple times or repeatedly on article 1 to endow it with the property of removing dirt, stains, oil stains, or other predetermined contaminants.

[0322] Photocatalytic self-cleaning fabrics use a variety of semiconductor materials, including titanium dioxide (TiO2), zinc oxide (ZnO), and silicon dioxide (SiO2), etc. TiO2 has three crystal forms: anatase, rutile, and brookite. TiO2 can be used as a photocatalytic hydrophilic pigment, which mainly consists of rutile phase and anatase phase.

[0323] Some pigments can also be applied to the article to form an anti-friction coating. The anti-friction coating can be composed of solid lubricants distributed on the article. Lubricating pigments can also enhance the corrosion resistance or flame retardancy of the article. The anti-friction coating can form a lubricating film covering all surface roughnesses, thereby optimizing the friction performance between metal-metal, metal-plastic, or plastic-plastic under extreme loads and working conditions. Examples of anti-friction pigments included in the coating include materials selected from the following non-exhaustive list: molybdenum sulfide (MoS), molybdenum disulfide (MoS2), polytetrafluoroethylene (PTFE), graphite, and special pigments. In addition, applying the pigments and the coating can improve the color fastness after article treatment or the touch of article 1.

[0324] Ultraviolet-absorbing or light-protecting pigments can contain mycosporine-like amino acids (MAAs). MAAs can block or absorb UV-A and UV-B and ultraviolet rays in the wavelength range of 310 nm to 360 nm. Melanin pigments can also be used for ultraviolet protection. In addition, carotenoids and photosensitive pigments can be used as light-protecting pigments because they have the function of quenching oxygen radicals. The carotenoids and photosensitive pigments can also be used to supplement photosynthetic pigments, which absorb light energy in the blue light region.

[0325] In another embodiment, the pigments used in the process for forming a coating or film on a workpiece may include metal oxides, such as at least one metal oxide selected from the group consisting of: SiO2, ZrO2, TiO2, Ta2O5, HfO2, ThO2, SnO2, VO2, In2O3, CeO2, CuO, CuS, FeCl2, ZnO, Nb2O5, V2O5, Al2O3, Sc2O3, Ce2O3, NiO, MgO, Y2O3, WO3, BaTiO3, Fe2O3, Fe3O4, Sr2O3, TiO3, Cr2O3, Mn2O3, Mn3O4, Cr3O4, MnO2, RuO2; or a composition of the above oxides formed, for example, by doping or mixing particles.

[0326] For coatings that need to be biocompatible, the coating can be adapted for in vitro applications and optionally can employ biopolymers as described herein. To achieve this property, the plasma monomers or precursors can include at least one of the following materials: collagen, fibrin, fibrinogen, platelet-rich plasma, alginate, gelatin, albumin, and hyaluronic acid.

[0327] Other materials that can be injected or supplied to the plasma region include the terpene β-elemene. In addition, cyclic monomers suitable for ring-opening polymerization (ROP) can be used. These monomers are optionally also suitable for ring-opening copolymerization (ROCOP). Such suitable materials can include one or more materials selected from the group consisting of: epoxides, cyclic trisiloxanes, cycloolefins, lactones, lactides, cyclic carbonates, and amino acid N-carboxyanhydrides.

[0328] It should be understood that both anionic ring-opening polymerization (AROP) and cationic ring-opening polymerization (CROP) can be achieved using plasma polymerization techniques. In addition, ring-opening metathesis polymerization (ROMP) can also be carried out through the use of plasma polymerization techniques.

[0329] In another embodiment, the system can be configured to perform pre-treatment or post-treatment on the workpiece. The pre-treatment or post-treatment can be any treatment process that can improve the interaction between the pigment and the plasma coating on the workpiece 1. Any pre-treatment or post-treatment can be implemented outside the system, but can be used as needed to optimize the performance of the plasma coating and the pigments contained therein. For example: a heat treatment process can be used to remove the moisture of the workpiece before processing, or to promote the curing of the plasma coating after processing through heat treatment. Other treatment processes can also be implemented, such as cleaning treatment, flushing treatment, ozone exposure, electrostatic cleaning, charging the workpiece, exposing the workpiece to predetermined radiation and / or light, or plasma treatment. The workpieces treated in this way can enhance the coating durability, the functional performance of the coating and / or the pigments in the coating, the coating hardness, the coating touch, the coating thickness, the color performance under the coating or the article, the coating appearance, or the coating gloss.

[0330] The system can also achieve single-sided or double-sided coating. For example, for single-sided coating of a substrate product, it can be achieved by a set of processing modules arranged towards one side of the product. This can be exemplified as Figure 1 shown, all processing of the substrate product is arranged towards the first side. If there are also some processing modules towards the second side of the substrate product, the processing of the second side of the product can be completed in the same process. Or, the first-side processing module can be configured to push, apply, or spread the coating from the first side of the product to the second side, so as to process the first side and the second side of product 1.

[0331] In another embodiment, the system can pass the product through the system and process the first side of the product, and adjust the module towards the second side of the product during secondary feeding so that the product is fed through the system for the second time. This operation can include flipping the product before secondary feeding, or repositioning one or more modules within the system to achieve the processing of the second side.

[0332] Since system 1 can perform multiple processing or single-sided processing on the product, the product can be given one or more different functional characteristics. For example: the first side of the substrate is hydrophobic-treated, while the second side of the substrate can have a hydrophilic coating. This is particularly advantageous if the substrate product has a porous property. The hydrophilic treatment can be used to achieve water adsorption and conduction, while the hydrophobic treatment can achieve water transport and rejection in a predetermined manner. In this way, a moisture-conducting system without multiple layers of film, bonding processes, and complex structures can be formed. Other effects are: applying a hydrophobic treatment layer on the first side of the substrate product, relatively overlaying a hydrophilic treatment layer on the hydrophobic treatment layer, and further applying a hydrophobic / hydrophilic treatment layer on the second side of the substrate product, so as to make the intermediate coating structure adapt to the moisture transport function.

[0333] In this specification, the term "treatment" can optionally be used interchangeably with the term "plasma polymerization coating". The term "pigment coating" herein refers to a coating containing pigments formed by plasma polymerization coating. Herein, the terms "precursor, chemical agent, or monomer" can be used interchangeably in each specific embodiment, and unless one or more types of monomers, chemical agents, or precursors need to be excluded, these terms are not construed restrictively.

[0334] Although specific pigment embodiments have been listed, the pigments involved in the foregoing applications can also be applicable to one or more other functional applications. Therefore, any pigment described herein can be used in other embodiments of the present disclosure as needed. The pigment particle size can optionally be nanoscale or micron-scale, and / or include a mixture of both.

[0335] Although the present invention has been described with reference to specific embodiments, those skilled in the art should understand that the present invention can also be implemented in many other forms without departing from the basic principles and purposes described herein.

[0336] The present invention and the preferred embodiments specifically include at least one technical feature with industrial applicability.

Claims

1. A system for coating an article, characterized in that, The system includes: a pigment applicator configured to apply a pigment; a plasma module configured to generate a plasma region; at least one of a chemical agent and a precursor supplied to the generated plasma, such that the plasma region can at least partially polymerize at least one of the chemical agent and the precursor to form a plasma polymerized coating; and wherein, the pigment is fixed to the article through the plasma polymerized coating.

2. The system according to claim 1, characterized in that, It further includes a post-plasma treatment module configured to treat the plasma polymerized coating.

3. The system according to claim 1 or 2, characterized in that, The pigment applicator is integrated with the plasma module.

4. The system according to any one of the preceding claims, characterized in that, The plasma module is housed in a chamber locally purified by a plasma gas to a purity exceeding 90%.

5. The system according to claim 4, wherein An inlet sealing roller is provided at the entrance of the chamber, such that while allowing the article to enter the chamber, the plasma gas is substantially maintained in the chamber and external fluid entry is restricted.

6. The system according to any one of the preceding claims, characterized in that, The pigment applied to the article is at least one of a colorant, a functional pigment, and a conductive pigment.

7. The system according to any one of the preceding claims, characterized in that, The plasma module is configured to supply at least one of a chemical agent and a precursor to the plasma region, such that at least one of the chemical agent and the precursor forms plasma polymerized molecules before being applied to the article to form a plasma polymerized coating.

8. An article with a plasma coating, characterized in that, The article includes: a surface on which the pigment is deposited, the pigment is combined with the article through the plasma polymerized coating, and the polymerization pressure of the plasma polymerized coating is between 95 kPa and 105 kPa.

9. The article with a plasma coating as claimed in claim 8, wherein, An additional pigment deposition layer is applied on the surface of the plasma polymerized coating.

10. The article with a plasma coating as described in claim 9, characterized in that, The additional pigment deposition layer is fixed to the plasma polymerized coating through an additional plasma polymerized coating.

11. The article according to any one of claims 8 to 10, characterized in that, The pigment is applied to the article during the plasma polymerization step, such that the pigment is combined inside the plasma polymerized coating when applied.

12. The article according to any one of claims 8 to 11, characterized in that, The particle size of the pigment is relatively larger than the thickness of the coating.

13. The article according to any one of claims 8 to 12, characterized in that, The pigment is a colorant, and its color is different from the color of the article itself, such that the whole article presents a chromaticity or a similar color to the pigment colorant.

14. The article according to any one of claims 8 to 13, characterized in that, The pigment is a functional pigment, and it can release ions and / or diffuse ions when combined inside the plasma polymerized coating.

15. The article according to any one of claims 8 to 14, characterized in that, The plasma polymerized coating is completed through a post-plasma treatment step to cure or treat the exposed surface of the plasma polymerized coating.

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