HK1227448A1 - Plasma treatments for coloration of textiles - Google Patents

Abstract

A method of treating a substrate, comprising providing a substrate having a generally sheet or planar form or a fiber or yarn form; providing a colorant to be set at the surface of the substrate; and subjecting the substrate and colorant to reactive species from a plasma generated by an atmospheric plasma apparatus until the colorant is set at the surface of the substrate. A method of setting a colorant on a substrate, comprising performing an etch operation, or plasma pre-treatment to change surface charge, on a substrate using a plasma, particularly a plasma generated at atmospheric conditions, to create a desired surface texture, or surface charge, at the surface of substrate; and depositing a colorant on the surface under plasma or non-plasma conditions; and allowing the colorant to set at the surface of the substrate.

Description

Plasma treatment for the coloration of textiles

RELATED APPLICATIONS

This application claims benefit and priority to U.S. provisional application serial No. 61/915,942 filed on 12/13/2013, the contents of which are hereby incorporated by reference as if fully set forth herein for all purposes.

Background

The present subject matter relates to colorants for fibers, textiles, and other substrates. The subject matter of the present invention relates in particular to the application of natural or synthetic colorants to textile surfaces. The subject invention may use plasma generated in an atmospheric pressure system to facilitate the coloration of a substrate.

The textile material may be in one of several forms such as a fiber, yarn, fabric, garment, and the like. Textile colorants are supplied both in solid form and in liquid form, for example, as a powder, granules, solution, or dispersion. In certain examples, the precursor is applied to the textile material to generate the colorant in situ within the textile.

Textile colorants impart color to textile materials, and are generally highly permanent as a result of their chemical bonding or physical entrapment (physicalen component) within or around the textile material. Both dyes and pigments are used for the coloration of textiles. The former substances are present in solution at some point during their application, while the pigments remain undissolved within any vehicle in which the pigment is applied, as well as within the textile material itself. The dye has affinity for the textile material and is soluble in a suitable solvent for application to a given substrate. The dye may penetrate the fiber to dye where the pigment is fixed to the surface. The dye is attracted to the fiber due to chemical interactions between the fiber and the dye. The reactive group attached to the chromophore (colored molecule) provides the ability of the dye to react with the fiber without affecting the color. The bond may be formed by hydrogen bonding, ionic bonding, or covalent bonding. Complex interactions and variables in staining are well documented. The areas of variability include substrates, chemicals, preparation of the substrates, and process variations.

The pigment imparts color; however, pigments do not have an inherent affinity for textile materials. When the dye can diffuse into the fiber material, the pigment is bound to the surface of the fiber. In some cases, the name may be distinguished by whether the colorant is suspended or dissolved in the solvent.

Current dye technology for textiles uses large amounts of water to apply the dye. The fabric must first be wetted to aid in the penetration of the dye into the fabric. These wetting processes also use a large amount of heat and energy to cure and set the dye. After the fabric is removed from the dye, the fabric is then heated to remove the moisture and permanently attach the dye to the fibers in the fabric. It is known that prior to the application of any dye, the fabric may be pre-treated via atmospheric plasma to condition or activate the fabric surface for improved dye pick-up (dye pick up) during typical wet processing. The color fastness, curing temperature reduction and wettability/hydrophilicity can each be improved after a suitable atmospheric plasma pretreatment. However, such pretreatments still use and suffer all the disadvantages of conventional water-tight bulk dye bath procedures. Due to the disadvantages of the water-carrier approach, other chemicals must be added to control the pH, alkalinity, and other parameters of the bath.

Traditionally, water has been used as a dyeing medium between fiber and dye interactions. Hydrophilic fibers absorb water (which breaks the internal fiber hydrogen bonds and causes the fiber to swell with water, which allows the dye to migrate into and bind with the fiber.

Application of the textile finish (finish) typically involves passing the fabric (woven, knitted or non-woven) through a chemical bath followed by a thermal curing process. In a chemical bath, the fabric collects or absorbs certain chemicals in the bath. These chemicals are commonly referred to as "finishes" and include water repellents, antimicrobials, UV protection, and colorants. To aid in the solubility of the chemical finish in the chemical bath, surfactants and emulsifiers are often added to produce a uniform suspension in the bath.

Currently, the wetting process used with textiles has several disadvantages. Drying and curing of the treated fabric requires that the fabric be exposed to elevated temperatures for several minutes. Large ovens and frames may be required to prevent fabric shrinkage, while high temperatures may change the drape and stiffen the fabric, or create a dry and rough hand. The additives required to solubilize the finish in the bath can penetrate the fabric, leaving the decomposed products, producing a film, or remaining as an impurity. Certain impurities may not wash off and result in the removal of finishes during certain household cleaning practices. Because the composition and pH of the chemical bath changes over time as the finish is absorbed onto the fabric, the bath must be periodically replaced. This is costly to the process and environment where the chemicals are used, if not properly filtered. Furthermore, the dye bath chemistry must be constantly monitored and adjusted. Large amounts of water and energy are used during these finishing processes to cure the fabric at relatively high temperatures. In addition, at each step of the process, there are specialized equipment and steps — baths, ovens, cleaning and circulation of baths and water. The equipment required for all the steps occupies a considerable floor space on the plant floor, increasing the complexity and expense of the operation.

Other areas where there is a need for efficient and easy construction of end products with a variety of properties include bedding, table linens, upholstery, draperies, tents, canopies, and the like.

Accordingly, there is a substantial need for improved textile colorant applications and constructions and manufacturing methods that address the aforementioned needs. These and various other needs are addressed by the subject matter of the invention disclosed herein.

SUMMARY

In general, the present subject matter relates to methods of treating substrates, such as textiles, to improve the properties of the substrates. In certain aspects, the present subject matter contemplates providing a substrate having a generally sheet or planar form.

In certain embodiments, the inventive subject matter relates to a method of treating a substrate comprising: providing a substrate having a generally sheet or planar form or a fiber or yarn form; providing a colorant to be solidified at a surface of the substrate; and subjecting the substrate and the colorant to reactive species from a plasma generated by an atmospheric plasma device until the colorant solidifies at the surface of the substrate.

In other embodiments, the inventive subject matter relates to a method of treating a textile, comprising: providing a textile; providing a colorant to be solidified at a surface of the textile; subjecting the textile and/or the colorant to plasma conditions sufficient to solidify colorant monomer at the surface; and continuing the conditions until the colorant solidifies.

In still other embodiments, the inventive subject matter relates to a method of solidifying a colorant on a substrate, comprising: performing an etching operation on the substrate using a plasma, in particular a plasma generated under atmospheric conditions, to produce a desired surface texture at a surface of the substrate; and depositing a colorant on the surface under plasma conditions or non-plasma conditions; and allowing the colorant to solidify at the surface of the substrate.

In yet other embodiments, the inventive subject matter is directed to a construct comprising a substrate material and a colorant solidified at a surface of the substrate, and wherein the substrate comprises a textile material having a substantially sheet or planar form, and the textile comprises an etched surface treatment layer and a composite of the colorant and the substrate material in the etched layer.

As used herein, "textile" is used in the broadest sense, i.e., a woven, knitted, felted, or other woven or non-woven thin sheet of a flexible material, such as a fabric or cloth, useful in finished articles such as articles of clothing, footwear, and interior trim. Textiles may be composed of synthetic fibers, natural fibers, blends, and bio-based fibrous materials. The textile may be used in any number of applications, including for casual wear, commercial apparel or uniforms, household goods, furniture or transportation upholstery, service items such as table cloths or napkins, carpets, felts, outdoor furniture, tarpaulins or sunshades, and any other fibrous item. The fabric may be a flexible, fibrous non-woven substrate, such as paper and paper bandages, disposable garments or handkerchiefs.

The class of plasma processing operations, referred to as "atmospheric plasma" processing, is particularly suitable for applying colorants to textiles in accordance with the inventive subject matter. Plasma operation promotes novel interactions of dyes or other colorants at the surface of the substrate to which the colorant is applied to visibly impart color.

The method of the present subject matter eliminates or substantially reduces the need for water throughout the dye process. The method also substantially reduces the energy required to heat the fabric to a high curing temperature, such as the energy currently required to permanently attach dyes to fabrics. Plasma dyeing does not require a large oven to remove water from the treated substrate. In addition, the solution reservoir for the dye solution will remain a constant solution and never be diluted-it is easier to add a large amount of solution than constantly adjust the dye bath chemistry in conventional current processes.

The process input of removing the dye bath also frees up a lot of processing space on the factory floor.

In other embodiments, a second application technique of the present subject matter involves applying a dye or other colorant directly to a fabric or other substrate via a pad process. The treated fabric is then subjected to a plasma process to cure the dye and permanently attach the dye to the fabric surface. The method will also advantageously substantially reduce the water and energy consumed relative to conventional water-based processes.

In general, the use of plasma to apply or cure dyes to fabrics will reduce processing time, reduce cost, and provide less burden to the environment. The process of the present invention comprises applying all colorants and dye types including synthetic dyes and organic dyes and blends of the two onto the surface of all substrates. Substrates include textiles comprising woven, non-woven, and knitted fabrics of synthetic, natural, and bio-based fibers, and any combination of each. The process of the present invention extends to the application of colorants to leather, synthetic leather and thermoplastics of the same composition for surface chemistry.

In certain embodiments, the inventive subject matter relates to a method of treating a textile, comprising: by ink jet printing, supercritical CO₂Dyeing or solution dyeing applies the colorant to the substrate; and subjecting the textile to reactive species from a plasma generated by an atmospheric plasma device until the colorant solidifies at the surface of the substrate.

These and other embodiments are described in the following detailed description and drawings.

The foregoing is not intended to be an exhaustive list of embodiments and features of the inventive subject matter. Other embodiments and features will be understood by those skilled in the art from the following detailed description taken in conjunction with the accompanying drawings.

The following is a description of various inventive routes that are under the subject of this invention. The appended claims, as originally filed in this document or as subsequently amended, are hereby incorporated into this summary section as if directly written.

Brief Description of Drawings

Unless mentioned as illustrating the prior art, the following figures illustrate embodiments according to the subject matter of the present invention.

Fig. 1 is a schematic representation of a prior art apparatus that may be used in a method according to the inventive subject matter that is suitable for treating a substrate with a colorant under plasma operation.

Fig. 2 is a perspective view of another possible embodiment of a prior art apparatus that may be suitable for use in a method according to the inventive subject matter for treating a substrate with a colorant under plasma operation.

Fig. 3 is a representation of a side view of the plasma processing apparatus shown in fig. 2.

Detailed Description

Overview

Those skilled in the art will recognize that many modifications and variations are possible in the details, materials, and arrangements of parts and actions which have been described and illustrated in order to explain the nature of the subject matter of this invention, and that such modifications and variations do not depart from the spirit and scope of the teachings and claims contained herein.

In certain of its possible embodiments, the present subject matter generally relates to applying a colorant to a surface of a substrate material to impart a desired color and color scheme (i.e., a combination of two or more different colors) to the substrate. By "applied to a surface," it is generally meant that the colorant is applied as a final bonded deposition material, or otherwise fixed at or embedded in a surface material of the substrate sufficient to enhance the appearance of the desired color at the surface of the substrate due, at least in part, to the colorant. The fixation of the colorant in a permanent or semi-permanent manner (i.e., capable of remaining substantially fixed through normal use and repeated conditions of laundering colored articles) may be referred to herein as "setting" of the colorant. Solidification of the colorant at the surface of the substrate means a deeper level on the surface and/or below the surface but with sufficient surface visibility to impart the desired color characteristics.

While much of the following description may be applicable to all types of colorants, dyes will be used as the primary example of a colorant to illustrate the subject matter of the present invention and the principles of operation.

Substrates specifically contemplated according to the inventive subject matter include textiles. The textile is not limited to any particular type. As used herein, "textile" is used in the broadest sense, i.e., a woven, knitted, felted, or other woven or non-woven thin sheet of a flexible material, such as a fabric or cloth, useful in finished articles such as articles of clothing, footwear, and upholstery. Textiles may be composed of synthetic fibers (typically petroleum-based), natural fibers, blends, and bio-based fibrous materials.

In certain of its possible embodiments, the subject matter of the present invention relates to the coloration of woven and non-woven textiles (which may also be referred to herein as "substrates") as substrates in plasma processing operations. The class of plasma processing operations known as "atmospheric plasma" processing is particularly suited to produce such modifications. The present subject matter specifically contemplates modification in properties of textiles to which a colorant is applied to a textile surface.

Current textile wetting processes are energy and resource intensive. Textile processes such as dyeing, water or stain repellency (water or stain repellency) and other surface treatments require large amounts of water and energy for dyeing and maintaining cure temperatures. Wet-dyeing equipment also has a large footprint on a factory floor. Accordingly, there is a need for an improved textile process that uses little or no water. There is also a need for such processes that require less energy and space, and less chemicals and by-products. Plasma processing can be used to impart properties such as dyeability and/or water and stain repellency by selecting plasma conditions that modify the surface of the substrate with respect to changing hydrophobicity/hydrophilicity. For example, a dye that is primarily hydrophobic will bind better to a substrate surface that has been modified to be more hydrophobic.

Plasma technology has existed at least since the 60's of the 20 th century. Plasma is generally considered to be a gaseous phase of matter characterized by excited species such as ions, free electrons, and some amount of visible, UV, and IR radiant energy. The plasma state may be generated by electrical, nuclear, thermal, mechanical, and/or radiant energy. Plasma can be characterized by charged particle density, temperature, pressure, and the presence/absence of electric and/or magnetic fields. Plasmas are generally classified as thermal or non-thermal. In a thermal plasma, temperatures of several thousand degrees are reached, which is destructive to textiles and other common materials. Non-thermal plasmas may be referred to as "cold" plasmas because they can be maintained at low temperatures, for example, in the range of 0-100 degrees celsius. There are two types of cold plasma that can be used in textile applications: low pressure, i.e., subatmospheric (about 1-100pa) and atmospheric (ambient) pressure.

Atmospheric plasmas are available in many different forms: corona treatment, dielectric barrier discharge, hybrid combinations, and atmospheric glow discharge. One advantage of low pressure plasma treatments is that they are performed in a closed vessel (contained vessel) under vacuum. They are therefore limited to batch processing of textiles, not continuous processing. Batch processing is not efficient for the speed at which textiles are processed in a roll-to-roll process for large volumes. On the other hand, with the recent advances in atmospheric plasma treatment, there is now the possibility of continuously processing textiles. Because atmospheric plasma treatment can be a roll-to-roll process and can simulate high temperature reactions at room temperature, it is promising as an ideal process for the modification of textiles.

Textiles often have limitations with respect to high curing temperatures and process temperatures. Although many parameters affect plasma processing (plasma gas type, residence time, gas flow, frequency, power, pressure, ambient temperature, liquid monomer, gas), the process is more energy efficient and environmentally friendly. A disadvantage of conventional high temperature plasma processes is that surface modification and molecular modification are limited by the aggressive nature of the plasma. The plasma breaks down the molecular chains of the molecules injected into the plasma and breaks up the material. The atmospheric plasma provides sufficient energy to create a coating that maintains the space between the yarns, withstands multiple home laundering, maintains the integrity of the fabric, and does not affect the air permeability of the fabric. The space between the fibers in the woven fabric is about 100nm, and a film thickness of 70nm will have a negligible effect on the air permeability of the fabric.

Ionized species in the plasma may be generated when a voltage is placed across the gas. The radicals present in the plasma react with the surface of the substrate and/or with other species in the plasma. The plasma reaction can transform the substrate surface in a variety of ways. The species and energy in the plasma may be used to etch or clean the substrate surface. The plasma can cause various forms of substrate surface activation. For example, plasma conditions may cause chemical bond cleavage; grafting of chemical moieties and functional groups, volatilization and removal of surface materials (etching), dissociation of surface contaminants/layers (cleaning/scrubbing), and deposition of conformal coatings. In all of these processes, a highly surface specific area of the textile material (e.g.,<1000A) Are given new desirable properties without adversely affecting the bulk properties of the constituent fibers or other constituent materials. To exemplify several textile applications, the surface may be roughened or smoothed. They can be made more hydrophobic or more hydrophilic. Chemical modification of the surface may occur by attaching functional groups to the substrate surface. Plasma polymerization of the film is also an option. During plasma processing, monomers or polymers can link together or polymerize at the substrate surface and provide thin film and technical property changes of various surfaces. Pretreatment and surface modification can be accomplished using only plasma gas/substrate interactions. To apply the thin film and functional groups, for example, a small amount of chemical is injected via a syringe, or via a mist into the plasma cloud, or as a mist onto the substrate surface, where the substrate then passes immediately under the plasma cloud. Some gas plasmas are used for some effects: argon-surface roughness modification; oxygen- -surface and surface energy modification; ammonia and carbon dioxide-surface chemical reactive modification. Inert gas plasmas using helium are particularly suitable for monomers that are polymerized via free radical reactions. The inert gas is capable of triggering polymerization without chemically altering the resulting polymer coating. The aforementioned reactive gas (H)₂、N₂、NH₃) The addition of (b) can alter the properties and composition of the resulting polymer. These blends can induce condensation reactions or crosslinking of the polymer chains. For example，H₂May lead to condensation of the monomers via loss of OH groups by means of a condensation reaction. Furthermore, to increase the durability of the monomer, N₂And NH₃May induce cross-linking of the polymer chains. Proposed routes to plasma-induced polymerization reactions induced between monomer-fabric or monomer-monomer polymerizations have been described in the literature. Plasma treatment has been studied by others for the application of water repellents and secondary finishes. Water repellents have been combined with flame retardants. The flame retardant and water repellent monomers are mixed in a bath and applied to the substrate. The finish is then simultaneously cured using an atmospheric glow discharge plasma. This study shows the potential for secondary finishes including water repellents, biocides, flame retardants, dye chemistries, etc., in feeds with protein monomers. Thus, the addition of one or more secondary functional finishes may be included in the dye or other colorant stock or in separately applied stocks. For example, secondary finishes in different raw materials may be added by atmospheric plasma via additional channels.

The following is one possible embodiment for applying the colorant to the textile substrate and then applying the optional secondary finish. In a first step pre-application step, a substrate, such as a fabric, is subjected to a plasma pre-treatment that activates the fabric surface. In a second step, a colorant, such as a dye or pigment, is applied in vapor form (or via padding addition) to the activated surface of the fabric. In a third step, the fabric surface with the applied colorant is subjected to a second plasma exposure. The multi-step process can be used to optimize colorant composition, e.g., dye stock solution composition, and plasma parameters, e.g., flow rate, etc., relative to a single-step process in which the fabric is passed through a plasma-dye mixture and allowed to deposit, bind the dye to the fabric in a single-step plasma treatment step. Further, under these processes, a secondary finish may optionally be added to the fabric and stock solution.

The plasma conditions are at about room temperature and at about atmospheric pressure. The dyes contemplated below may be injected into the plasma chamber as a liquid spray or vapor or atomized particles and are expected to withstand plasma process conditions. When plasma is generated by voltage addition, active species are generated that collide with the textile surface. For textiles, the plasma typically reacts with carbon or heteroatoms of the substrate and can form reactive free radical functional groups. When a colorant, such as a dye molecule, is injected into the plasma, the colorant should bind and cure to the active surface groups of the substrate via chemical bonding.

For fabrics and similar substrates, since the atmospheric plasma is at about room conditions, it is not necessary to precondition the fabric for the humidity of the air. In certain possible embodiments, the general process involves moving the fabric into a plasma chamber and subjecting the fabric to a dye at atmospheric pressure, then rapidly solidifying the dye on the fabric surface by the plasma to achieve a uniform coating that does not affect the drape or breathability of the fabric. The amount of dye deposited (and/or solidified) may depend on the flow rate of the dye in the chamber under plasma conditions as well as the staged velocity or residence time. The change in time spent in the chamber under plasma conditions can increase the colorant saturation of the colorant at the surface of the substrate. In addition, the process may be repeated multiple times to increase the concentration of the colorant to impart desired color properties without affecting the drape or stiffness of the fabric.

Generally, the plasma can generate transient activating species on the substrate surface. Since atmospheric plasma operation uses radical chemistry at room temperature, the dye is expected to remain stable during plasma operation. However, it is possible that the colorant itself may become activated in the plasma. For example, if both the dye and the fabric substrate are activated by plasma, the free radicals from each material may bind to each other. If activation of the dye becomes problematic or destroys the dye material, it will be possible to alter the feed gas to specifically target radical formation. Another possibility is to deposit the dye and use the reactive species from the plasma as an agent to bind the dye molecules and the substrate together.

In short, the electric field of the plasma or the active species generated by the electric field of the plasma device may generate specific active groups and selectively form the active groups on the dye dispersed in the plasma or on the substrate communicating with the plasma or the active species of the plasma. The plasma may be used to generate reactive species, such as hydroxyl, amine, peroxide, on the dye molecules and/or on the surface of the substrate.

While atmospheric pressure plasmas typically use helium (e.g., for polymer deposition) as a carrier gas, other gases or blends may be used. However, helium is a small atom that may not have enough vibrational, electronic, and rotational energy levels to cause high ionization. Other gases may be used as carrier gases in generating relatively high energy plasmas. Such gases include ambient air, nitrogen, oxygen, argon, and any combination of these gases. These other carrier gases require relatively high voltages and may damage the textile substrate, so the gases and process conditions will be selected accordingly.

Dye classes, mechanisms and applications

In certain embodiments, the inventive subject matter relates to methods of applying a colorant, such as a dye, onto or into the surface of a textile material or other substrate such that the colorant visibly imparts color to the surface.

Most dye classes are expected to be maintained under plasma conditions and formed as reactive plasma species. Under plasma, most dye classes are expected to be sufficiently energetic to be made into reactive species without degradation. Alternatively or in addition, the substrate surface will be subjected to plasma and become activated by the plasma, and the dye, in plasma activated or unactivated form, will be cured on the substrate in the plasma.

Dye chemistry can be categorized by chemical composition and application of the dye to a particular fiber. For example, a variety of chemistries are classified according to acid dyes, basic dyes, disperse dyes, direct dyes or direct dyed dyes (direct or substentive), mordant and chromium dyes, pigments, organic dyes, solvent dyes, azo dyes, sulfur dyes, rayon acetate dyes, nylon dyes, cellulose acetate dyes, and vat dyes. For cellulose fibers, these application methods include: direct dyes, sulfur dyes, azo dyes, reactive dyes, and vat dyes. Protein and synthetic fibers use acid, basic and disperse dye application methods. The dyes used for each application were further classified into 13 groups according to their chemical structure: azo dyes, anthraquinone dyes, benzodifuranone dyes, polycyclic aromatic carbonyl dyes, indigoid dyes, polymethine and related dyes, styryl dyes, diarylcarbonium dyes and triarylcarbonium dyes, phthalocyanine dyes, quinophthalone dyes, sulphur dyes, nitro and nitroso dyes and also hybrid dyes.

Acid dyes contain an acid reactive group: -SO₃H, and is suitable for use with compounds containing basic groups such as free amino groups: -NH₂The fibres comprise the amino acids proline and 18 α -amino acid, some of which contain acid and basic groups the main dye absorption site is an amino acid group, as wool is amphoteric it can absorb acid or basic dyes nylon also has amino groups, however, the number of these end groups depends on how the fibres are made and on the molecular weight₃H。

Disperse dyes are almost insoluble in water. These dyes can be applied to nylon, cellulose acetate and other fibers. However, disperse dyes are generally suitable for hydrophobic fibers such as polyesters. A dispersant is used in the dye bath to help disperse the insoluble dye and increase the rate of dye absorption. The carrier may also help to increase the affinity for the polyester, as well as to change the size of the dye molecules to increase diffusion. These changes can also alter dye fastness to the fiber. For example, a dye bath with high water temperature (e.g., about 140 ℃) may help the diffusion of larger dye molecules into the fiber. This thermal process helps to provide better color fastness.

Polypropylene is hydrophobic due to its low surface energy. Polypropylene has poor hydrophilicity and is not reactive with cationic dyes. Pretreatment of polypropylene with oxygen plasma can incorporate oxygen onto the surface of the material in the form of C-O and O-H sites. These sites increase the dye uptake of the polypropylene from the cationic (basic) dye. Similarly, pre-treating the fabric with nitrogen can create N-H groups on the surface of the material, increasing the dye uptake (dyeexhaustion) from direct dyes (anionic dyes). Pretreatment of wool/polyester blends in nitrogen plasma and air plasma can induce NH₂A group, resulting in an increased uptake of anionic dyes (acid dyes). Using gas plasma pretreatment of oxygen/nitrogen/air, wool/polyester blends can show an increase in basic dye uptake by forming reactive COO-and OH-groups.

The successful application of a colorant to a fiber depends on the affinity of a given colorant for a given substrate. Because of this, the colorant is modified to specifically bind to the charge of the fibers, with an affinity for the fibers that is greater than the affinity for the carrier solution in which the colorant is suspended or dissolved. Each colorant has a complementary molecular design to bind with a given fiber. The colorant molecules are selected or designed to take into account a number of factors, including affinity for the substrate, durability to laundering, UV resistance, and other parameters required for each particular product end-use. While the following is a basic overview, it should be appreciated that many dye mechanisms may be modified to bind to the fibers, not listed below. Additional chemicals may be added to the dye solution to alter the reaction that allows, for example, acid dyes to dye fibers that are typically alkali dyed, and basic dyes to dye fibers that are typically acid dyed, and so forth. The following is a basic overview of the dyeing mechanism and how the plasma process can replace the current dyeing process using water as a carrier.

Polyester:

Disperse dyes can be used to dye polyesters. Disperse dyes are designed to be hydrophobic in nature. In this way, the dye is readily absorbed onto the hydrophobic surface of the polyester (i.e., like dissolving or the like). These dyes will generally not work with hydrophilic polymers such as cellulose (cotton). The following are structures of three basic disperse dyes. These dyes are usually azo, compounds having a group R-N ═ N-R' or compounds having the formula C₁₄H₈O₂The anthraquinone compound of (1).

Nylon and protein

Dyes for nylon and protein fibers typically form ionic bonds within the polymer of the fiber. An ionic bond is a bond between two ions of opposite charge. Polymeric fibers based on nylon, wool, and other proteins carry a positive charge (called cations). Thus, the dye must carry a negative charge to be attracted to and bind with the positive charge of the molecules on the fiber, and vice versa. The dyes used for these fibers are known as acid dyes. Acid dyes are generally not capable of binding to cellulosic substrates because the dyes are not capable of forming strong ionic bonds with them. This charge-dependent binding process is illustrated in the following figures. This bond is similar to that in table salt. The following is an exemplary dyeing mechanism for the charge-dependent binding process of dyes on nylon.

The following are basic formulas for acid black and alkali red dyes.

The basic dye is bound to the polymer backbone of the fiber having a negative charge. The polyester will not form an ionic bond with the positively charged basic dye due to charge repulsion. However, wool and silk each have a carboxylate group (-CO)₂). The carboxyl group carries a negative charge that will form an ionic bond with the positively charged dye molecule.

Cellulose fiber

Cellulose fibers such as: cotton, rayon, and linen are hydrophilic. Cellulosic dyes generally need to be hydrophilic (like attraction and the like) as opposed to polyester fibers, which are hydrophobic. Neither cellulose nor polyester fibers have strongly charged molecules that can form ionic bonds with dye molecules. In contrast, the affinity of the dye for the fiber is determined by electrostatic forces known as hydrogen bonding. This is a strong force in which the molecule possesses a partial charge (dipole moment) generated by the atoms contained within the molecule. These charges interact with oppositely charged dipoles of adjacent molecules. The bond is only an attractive force and the molecules do not share electrons. The following are examples, the cellulose fibers (a) are hydrogen bonded to the direct dye (B).

Classes of dyes for cellulosic fibers include azo dyes, vat dyes, sulfur dyes, direct dyes, and reactive dyes. Each of these dyes must generally be water soluble. Because the dye molecules can form hydrogen bonds, they are solubilized in water. Water has a dipole moment and is partially charged. Because of this, water can form and disrupt hydrogen bonds. Thus, water is a good solvent for many chemicals and can surround dye molecules, suspending them in solution. Hydrogen bonding on the dye molecules is then directed to the fiber as the water is evaporated.

Current research has shown that applying a cationic agent to cotton can change the charge on the cotton from negative to positive. This increases the affinity of the anionic dye. Currently, cationic agents are applied to lint in bale form and then blended with untreated cotton at a wool mill (yarn mill) to produce yarn, where the treated cotton can be dyed without the use of electrolytes (salts) or alkali (soda ash) and at low to warm temperatures. Current batch processing is expensive and only used for novel yarns (e.g., overprint leather, etc.). With this process, which uses atmospheric plasma commercially, there is a possibility of having a very large impact on both the cost and environmental aspects of dyed cotton. (reference: Cotton Incorporated Technical Bulletin: "Dyeing Cationic Pretreated cottonTRI 3016). Spraying dyes onto cationic cotton substrates using cationically treated cotton yarns and yarns treated with different levels of cations and curing in plasma, in accordance with the present subject matter, can help reduce the water and heat required. Another advantage is that the novel process should also provide better shade distribution and depth of dyeing.

To increase the color fastness (prevent the dye from being washed off), vat, sulfur and reactive dyes are produced. Each with unique processes outlined elsewhere. Reactive dyes have been modified to form covalent bonds with the fibers. Covalent bonds are equilibrium bonds in which electron pairs are shared. The following are general structures of the sulfur dye (a), the vat dye (b), the azo dye (c), and the reactive dye (d).

Each group of dyes has important substituents that allow the dyes to be soluble in water or to bind to hydrophobic/hydrophilic surfaces.

The plasma may assist the aforementioned dye-substrate interaction. Previously, water was the carrier fluid to allow the dye molecules to be solubilized or dispersed by hydrogen bonding to prevent agglutination of the dye molecules. In the case of plasma, the interaction of the plasma feed can modify the fiber surface to be more hydrophilic and hydrophobic. When the plasma generates a surface charge on the fiber, this creates an affinity for the dye molecules to bind via hydrogen, ionic, or covalent bonds. When the dye is injected as a fine mist onto the substrate or into the plasma, the dye molecules in the plasma cloud or on the substrate surface will have a uniform distribution. The dyeing process is the interaction of each dye molecule with a site on the fiber. Thus, each bond can be considered a single item, similar to a dye bath, and the amount of dye molecules sprayed on the substrate or directly into the plasma cloud will be effective to dye the substrate. Thus, if a plasma dyeing process is used, no water is required to perform most of the dyeing operation. After the addition of the dye to the fabric, the fabric requires heat curing to remove excess water from the fibers. Removal of excess water allows the dye molecules to adhere only to the polymer chains. However, the plasma process does not use any water. Therefore, thermal curing is not required. In addition, the plasma reaction can simulate a high temperature reaction. Thus, if any energy is required to overcome the bond energy to solidify or permanently fix the dye on the substrate, the plasma energy will be sufficient.

In addition, the basic chemical structure within each dye type is similar in that it has the same basic structure that will be bound to a particular fiber. The similarity between the charges of different fibers has been outlined herein. Thus, within accuracy, the binding results of the dye will be similar in any medium, water or plasma, since the reactions and bonds are similar.

For example, the following two tables show the structures of anthraquinone and aminoazobenzene based disperse dyes. The substituents R1-R7 control the properties, color, fastness and dyeing properties of the disperse dye product. Many dyes using water require a dye bath that balances many parameters: ph, alkalinity, and temperature, to name a few. Because the plasma does not use water, it is believed that the plasma can reduce the need for many chemicals and directly activate and attach colorants to the fibers.

1.http://monographs.iarc.fr/ENG/Monographs/vol99/mono99-7.pdf

2.J.R.Aspland,Textile Dyeing and Coloration,American

Association For Textile Chemists and Colorists

In the context of the present subject matter, the coloring reaction using dyes also allows secondary finish molecules to be attached to natural and synthetic materials to produce coating materials tailored for specific applications, such as colored garments and textiles for footwear, having highly reactive surfaces that provide UV-blocking properties, antimicrobial properties, and/or self-cleaning properties. The coating may be doped to provide electrical conductivity to the coating or selected portions thereof. One example of a dopant is iodine and various conductive metals. By selected doping, conductive circuits or conductive tracks can be formed in coatings for electronics and for computing or wireless applications, such as occurs in the field of "smart clothing".

Plasma processing

Plasma is generally considered to be a gaseous phase of matter characterized by excited species such as ions, free electrons, and some amount of visible, UV, and IR radiant energy. The plasma state may be generated by electrical, nuclear, thermal, mechanical, and/or radiant energy. Plasma can be characterized by charged particle density, temperature, pressure, and the presence/absence of electric and/or magnetic fields. Plasmas are generally classified as thermal or non-thermal. In a thermal plasma, temperatures of several thousand degrees are reached, which is destructive to textiles and other common materials. Non-thermal plasmas may be referred to as "cold" plasmas because they can be maintained at low temperatures, for example, in the range of 0-100 degrees celsius. There are two types of cold plasma operation that can be used in textile applications: low pressure, i.e., subatmospheric (about 1-100pa) and atmospheric (ambient) pressure.

Atmospheric plasmas are available in many different forms: corona treatment, dielectric barrier discharge, hybrid combinations, and atmospheric glow discharge. One advantage of low pressure plasma treatments is that they are performed in a closed vessel under vacuum. They are therefore limited to batch processing of textiles, not continuous processing. Batch processing is not efficient for the speed at which textiles are processed in a roll-to-roll process for large volumes. On the other hand, with the recent advances in atmospheric plasma treatment, there is now the possibility of continuously processing textiles. This is a novel and advantageous process for the modification of textiles, since atmospheric plasma can be a roll-to-roll process and can simulate high temperature reactions at room temperature, and requires little or no water.

When a voltage is placed across the gas, ionized species are generated in the plasma. The radicals present in the plasma react with the surface of the substrate and/or with other species in the plasma. The plasma reaction can transform the substrate surface in a variety of ways. The species and energy in the plasma may be used to etch or clean the substrate surface. The plasma may cause various forms of substrate surface activation. For example, plasma conditions may cause chemical bond cleavage; grafting of chemical moieties and functional groups, volatilization and removal of surface materials (etching), dissociation of surface contaminants/layers (cleaning/scrubbing), and deposition of conformal coatings. In all of these processes, highly surface specific areas of the textile material (e.g., <1000A) are given new desirable properties without negatively affecting the overall properties of the constituent fibers or other constituent materials. To exemplify several textile applications, the surface may be roughened or smoothed. They can be made more hydrophobic or more hydrophilic. Chemical modification of the surface may occur by attaching functional groups to the substrate surface. Plasma polymerization of the film is also an option. During plasma processing, monomers or polymers can link together or polymerize at the substrate surface and provide thin film and technical property changes of various surfaces. Pretreatment and surface modification can be accomplished using only plasma gas/substrate interactions. To apply the film and functional groups, for example, a small amount of chemical is injected via a syringe into, or via a mist into, the plasma cloud. Some gas plasmas are used for some effects: argon-surface roughness modification; oxygen- -surface and surface energy modification; ammonia and carbon dioxide-surface chemical reactive modification.

Different feed gases may produce different reactive species on the surface of the textile that will react or interact with the colorant molecules. For example, the formation of certain reactive species may increase the wettability and diffusion of different water and dye molecules into and onto the surface of the fiber. Whereas pretreatment of fabrics with atmospheric plasma has been used to improve the dyeing process. In certain embodiments, the inventive subject matter relates to novel methods that use atmospheric plasma to apply dyes or other colorants directly to the surface of a fabric, as well as to impart dye molecules of a certain molecular weight into the fiber and cure the colorants. This produces a permanent, wash-resistant color on and within the fiber without affecting the drape and soft hand of the fabric surface.

The plasma treatment is a dry process that does not require any significant amount of water (other than, for example, the dye material in which the dye or other colorant is solubilized or dispersed). Atmospheric plasma uses little energy and does not require heat to cure. The plasma can alter the surface properties of the textile and thus the dyeability. This alters or creates hydrophilic/hydrophobic sites on the textile, for example. It may also generate free radicals on the fiber surface that may react or interact with the colorant molecules. If a plasma etching process is used, it can open pores in the fiber to allow deeper penetration of dye molecules into the textile for better fastness.

U.S. patent publication 20080107822 relates to the treatment of fibrous materials using atmospheric pressure plasma polymerization and is hereby incorporated by reference in its entirety for all purposes consistent with the teachings herein. The disclosed systems and methods may be suitable for applying colorants to textiles. Fig. 2-3, consistent with the' 822 patent publication and discussed in more detail below, illustrate examples of suitable systems.

U.S. patent 8,361,276 discloses a method and system for large area, atmospheric pressure plasma for downstream processing and is hereby incorporated by reference in its entirety for all purposes consistent with the teachings herein. The system and method in this patent may be adapted for applying a colorant to a textile. Figures 2-3, consistent with this patent and discussed in more detail below, illustrate examples of suitable systems. The system may include an arc-free atmospheric pressure plasma generating device capable of generating at about 0.1W/cm³And about 200W/cm³A large-area, temperature-controllable, stable discharge is produced at a power density in between, while having an operating gas temperature of less than 50 degrees celsius. The device generates an active chemical species (which may also be referred to herein as a "reactive species"). The reactive species may include gaseous metastable species (radicals) and free radicals. As examples, such materials may be used for polymerization (e.g., free radical induced polymerization or polymerization by dehydrogenation-based), surface cleaning and modification, etching, adhesion promotion, and sterilization. For example, the system may include a cooled RF-driven electrode or a cooled ground electrode, or both cooled electrodes, wherein the active components of the plasma may be directed out of the plasma and onto the inner or outer substrate with or without simultaneous exposure of the materials to the electric field or ionic components of the plasma.

In certain embodiments, the inventive subject matter relates to an apparatus for generating an atmospheric pressure plasma at about 0.1W/cm³And 200W/cm³At power densities in between, produce large-area, non-thermal, stable discharges (discharges), but can also have neutral gas temperatures of up to about 50 ℃. Hereinafter, the term "atmospheric pressure" means a pressure between about 500 torr and about 1000 torr. The active chemical species or active physical species of the plasma exit the plasma discharge and then strike a substrate disposed outside of the discharge, thereby allowing the substrate surface to be processed without simultaneously exposing the substrate to the electric field or ionic components of the plasma. As stated, the plasma has a neutral gas temperature of less than about 50 ℃ even during extended and continuous operation, and by way of example, species containing gaseous metastable species and radicals may be generated. High power density, lower operating plasma temperature, and placement of materials to be processed outside of the plasma allow for accelerated processing rates and treatment of most substrates. As examples, plasma sources may be used for polymerization (e.g., free radical induced polymerization or polymerization by dehydrogenation based), surface cleaning and modification, etching, adhesion promotion, and sterilization.

In certain embodiments, the inventive subject matter relates to the steps of: coating the surface of a base textile material with at least one silk polypeptide that is a monomeric precursor to a polymer having selected properties; and exposing the coated substrate to an active species generated in an atmospheric pressure inert gas plasma, whereby the at least one monomeric precursor is polymerized, thereby forming a finish having selected characteristics. The monomer may be sprayed onto the substrate and introduced into the plasma chamber to cure. Or the monomer may be applied while the substrate is in the plasma chamber.

Pulsed or non-pulsed high power plasma can be used to produce durable coatings that can be applied using plasma exposures of seconds or less (as opposed to minutes) and to produce coatings that are comparable to those of the prior artThe continuously applied, effective power density of thicker, more durable coatings of those described may be in the range of 1W/cm²And 5W/cm²In (this is 10 of the power density reported for the prior art plasma)²Multiple and 10⁴Between multiples). The range of effective RF frequencies may include any ac frequency that, when capacitively coupled to the electrode, creates a "sheath" or dark space near the electrode. Typical frequencies may be between 40kHz and 100 MHz.

According to the inventive subject matter, a dye or other colorant material may be deposited onto the fabric outside of the plasma region, and the coated fabric or other substrate is then moved into an inert gas plasma, wherein products generated in the plasma, such as metastable species and ionic species, induce the dye to chemically bond to the fabric. The reaction process may have most of the breakthrough effects atypical of plasma processes; that is, the reaction starts on the substrate surface and propagates into the surface into which the dye may have diffused.

According to the subject of the invention, the use of an atmospheric gas plasma, such as a helium plasma, as an example, avoids chemical attack or degradation of the applied colorant by fragmentation. Notably, the atmospheric conditions thermalize ions generated in the plasma. Thus, the metastable species and ionic species generated in the plasma are effective to induce the reaction while otherwise remaining chemically unreactive. Other possible inert carrier gases include argon, krypton, neon, and xenon may also be used as the inert plasma gas.

It is well known that increasing the power applied to the plasma increases the thickness of the sheath or "dark space" surrounding the electrode. In a capacitively coupled plasma, such as the capacitively coupled plasma of the claimed invention, the sheath has a time-averaged electric field that repels electrons. Thus, it appears dark to the eye because it has a substantially reduced concentration of electrons that produce visible emissions from gas phase species by excitation via electron impact. This reduced level of electron density in the sheath inhibits dissociation of the fluorocarbon monomer. Neutral metastable species formed in the inert gas plasma may readily cross the voltage drop of the sheath and induce reactive species and reactions.

Electrons can only pass through the sheath for a short portion of the RF cycle and do so only to the extent necessary to maintain charge equalization. The positively charged ions pass through the sheath and will strike the substrate with sufficient energy (10-100eV) in a vacuum-based plasma to break up the molecules, rather than simply creating reactive species. Thus, according to the subject matter of the present invention, the textile may be held within the sheath region by placing it against or in close proximity to the electrode, wherein the high power applied to the plasma generates a large number of metastable species that may be used to initiate the exit of reactive species from the colorant condensed on the fabric, while avoiding fragmentation of the colorant due to energetic impingement of electrons or ions. In addition, if the substrate is held tightly against the electrodes, the plasma treatment process for woven textiles and nonwovens may be generally limited to the plasma-facing side of the substrate. Thus, the selected treatment may be applied to one or both sides of the fabric using the desired feedstock and carrier gas plasma to induce the reaction.

Furthermore, unlike vacuum-based plasmas, where a high DC bias is generated in the sheath region, atmospheric plasmas effectively eliminate the bombardment of energetic ions passing through the monomer to the substrate, which would have the same destructive effect as electron impact. That is, in an atmospheric pressure plasma, ions undergo frequent collisions with neutral gas phase species, and therefore do not gain kinetic energy that would otherwise be formed in a plasma operating under vacuum. In atmospheric pressure plasmas, ions are thermalized to near room temperature (about 0.03eV, as opposed to between 10eV and 100eV for vacuum-based plasmas), rendering such species unable to provide destructive collisions. Furthermore, the atmospheric plasma source here is a "symmetric" plasma; i.e. the areas of the parallel RF-driven and ground electrodes are equalAnd there are no grounded chamber walls that cause electrical behavior of the plasma. Thus, there is no DC bias and the power density may be higher than that set forth in the vacuum-based plasma of U.S. patent application publication No. 2004/0152381>10⁴And (4) doubling. As used herein, an "atmospheric pressure" plasma is defined as operating the plasma at a total gas pressure sufficiently high to create a plasma sheath in which collisions are effective to thermalize ions passing through the sheath. Typically, this occurs at pressures between 300 torr and 3000 torr. It is contemplated that pressures between 600 torr and 800 torr will typically be employed.

The use of an inert carrier gas plasma such as helium is most suitable for the colorant to be converted into a substance having free radicals. The inert gas plasma has the advantage of being able to trigger the radical reaction process without chemically modifying the colorant. However, in some cases, as an example, it may be advantageous to use a smaller amount of a reactive gas such as H₂、N₂、NH₃Or CF₄To inert gas to alter the properties, properties or composition of the substrate, colorant and/or the composite of substrate and colorant. The use of such gases in amounts typically less than 20% of the total gas flow can be used to drive other forms of polymerization, such as condensation reactions or cross-linking between polymer chains.

Certain colorants can be in the nature of monomers that form a polymerized coating on the surface of the substrate. H₂May help to promote the polymerization of such monomers that require loss of-OH groups by condensation reactions. Similarly, N₂Or NH₃The use of (b) may facilitate cross-linking of the polymer chains, resulting in greater durability of the resulting polymer.

According to certain possible embodiments of the inventive subject matter, a separate process module operating at atmospheric pressure may be used for: (1) condensing the colorant on the substrate; and (2) exposing the condensate to an atmospheric pressure plasma. Alternatively, the condensation of the colorant and the plasma process may be accomplished in the same module, rather than in separate modules. Typically, this will mean maintaining a constant outward flow of helium or other inert carrier gas in order to keep the colorant vapor away from the plasma region. The dual module process has the benefit of providing fastness or durability of the colorant on the substrate, as well as avoiding unwanted colorant vapor deposition on the electrodes of the plasma system. Under such systems, the textile treatment system can be operated continuously and with less maintenance than where vapor deposited species are formed in the plasma because no deposits form on the electrodes.

Examples of textile materials include, but are not limited to, textiles made from fibers of animal or plant origin, such as wool, silk, collagen, cotton, and other celluloses, synthetic fibers such as polyolefin fibers, polyesters, polyamides (i.e., nylons), fibers from liquid crystal polymers (e.g., aramids), polyoxymethylene, polyacrylic acid (i.e., polyacrylonitrile), poly (phenylene sulfide), poly (vinyl alcohol), poly (ether ketone) (i.e., PEEK), poly [2,2'- (m-phenylene) -5,5' -bibenzoimidazole ] (i.e., PBI), poly (glycolic acid-co-L-lactic acid), and poly (L-lactide), aromatic polyhydrazides, aromatic polyazomethines, aromatic polyimides, poly (ethylene imine), poly (ethylene glycol), poly (, Poly (butene-1), polycarbonate, polystyrene, and polytetrafluoroethylene, and combinations of the foregoing. Such combinations may allow for enhancement of certain desired fiber properties as well as certain aesthetic coloring results by dyes cured on different combinations of fibers in the substrate. Typically, a textile material or other substrate will be provided and processed into a sheet form or other planar form of the material. However, the substrate subjected to coloring under plasma treatment may also be a fiber or yarn used in weaving or knitting textiles. However, one skilled in the art will appreciate that other substrates may include yarns, threads, fibers, and other such filamentary materials; films and membranes, for example, those that function as complete, partial, or selective barriers to control environmental conditions such as water resistance, air permeability, and/or wind resistance. An example of a waterproof, breathable membrane material is expanded PTFE, which may be sold under the trade name GoreTex.

In addition to a substrate having a planar form or a sheet form or a filament form, the substrate may have a volumetric 3D form. For example, the form may be material on a last that represents some or all of the volume of the last. The base may be a backpack or other item for holding items. The substrate in planar, filamentary or 3D form may be a foam object used in the construction of footwear, apparel, backpacks and other carriers, furniture or upholstery, etc. The foam material comprises EVA and PU. The substrate may likewise be any natural or synthetic rubber or leather.

The complex of colorant and substrate contemplated herein may be referred to herein as a "construct". The colorant may be attached to the underlying substrate in the construct by any known chemical or bonding forces, including covalent bonding, hydrogen bonding, van der waals forces, ionic bonding, and physical entrapment. The colorant may be applied in a uniform thickness or in different thicknesses. In the case of a polymer coating, the monomer units form a monolithic structure on the lower portion of the substrate. In other cases, the monomer does not necessarily bind the monomer to the monomer, but rather binds the monomer to the substrate reactive sites to form a permanent coating on the underlying portion of the substrate. (in other words, the monomer is not in the form of a monomer but is a reactant combined with the substrate.) in the case of a variable thickness coating, the thickness of the coating can be considered as the average thickness over the surface. For many applications, the coating has a thickness between 1nm and 1mm or 10nm and 100 μm, or between 40nm and 50 μm, or between 0.5 μm and 10 μm, or between 1.0 μm and 5 μm. These ranges are representative and the subject matter of the present disclosure encompasses a wide range of thicknesses and is not intended to be limited to a particular given embodiment.

The applied colorant will generally be applied coextensively with the desired surface area of the substrate. In other words, the application area will generally correspond to the entire surface area selected. However, this is not to say that the entire area is covered with a real or continuous area of coverage. For example, in the case of coatings, they may have properties such as a mesh, a porous membrane, a network of regularly spaced perforations, or other non-solid patterns that are generally coextensive with the defined surface area. The coating may have a different topology, with some regions being thicker than others. The coating may also include two-dimensional features or three-dimensional features. For example, microelectronic devices, sensors, circuits, or traces may be integrated into the coating to provide functional features.

The colorant, as an integrated or dispersed molecule in the surface of the substrate or as a discrete layer, i.e., coating, may be applied in any desired pattern or color design. For example, a screen may be applied over the substrate to create a desired pattern for applying one or more colorants of the same or different colors. For a particular color effect, for example, a screen may be placed in front of the spray system (between the sprayer and the substrate) to produce a patterned spray on the substrate prior to curing. For certain designs of certain repeating patterns, for example, a roller may be attached to the front of the sprayer to change the colored pattern, where the repetition is the size of the roller diameter. Thereafter, the substrate may be reprocessed with a different screen and a different colorant to create a multi-colored pattern on the substrate. In addition, the nozzles may be arranged to each have a different colorant. The colorants may be applied sequentially in a single plasma operation or in separate batch operations.

Depending on the desired output of the multi-color design and the pattern, which may or may not be repeated, it is contemplated that the substrate may be colored by a printing process, such as an inkjet printing process, prior to plasma curing. After exiting the inkjet printer, typically in roll-to-roll form, the fabric may undergo a slight IR flash cure to prevent expulsion from the roll prior to plasma curing. The dye or other colorant is then permanently cured in the plasma. In some cases, for faster processes, the substrate may be run through an inkjet printer or other printing device and directly into the plasma for immediate curing.

It is also contemplated that the dye-containing solution may contain other elements within the dye to alter the substrate properties. The prior art has shown the ability to cure both water repellents and antimicrobial finishes in atmospheric plasmas. As an example of this, the solution may contain dye colorants necessary to dye the substrate, protein monomers, and water repellent chemicals that are sprayed onto the fabric and then cured in a plasma. The process may be in a jetting system or after applying the inkjet dye to the substrate described in the preceding paragraph. The present subject matter contemplates that any combination of performance finishes (water repellents, flame retardants, biocides, wicking agents, protein deposits, etc.), both known and yet to be discovered, may be included with the dye solution and applied simultaneously with the dye or continuously with the dye process to be cured in the atmospheric plasma with the dye.

For garment applications, the treated surface area will generally be at least 6 square inches, but may generally be more or less dependent on the desired end result. For batch processed rolls of material for apparel applications, the width of the coated surface area of the roll material will typically be at least between about 50-72 inches and its length will typically be between about 1-100 meters. The roll length depends on the fabric material and construction. For example, the fleece will be fluffy and transported in rolls of short length, whereas 10-20 denier down-cloth (down proof fabric) may be transported in rolls of higher length. For apparel applications, such materials may be used, in whole or in part, for the outer, middle, and/or inner layers of an article of apparel.

Turning now to FIG. 1, a schematic representation of a perspective view of one embodiment of an apparatus 10 for inert gas atmospheric plasma polymerization processing of a substrate is shown. A container 12, which may be heated or unheated, contains a material 13, for example, a material including at least one colorant plus any desired additives. The feedstock is drawn out of the vessel 12 through a heated or unheated tube 16, wherein a valve 18 is inserted into a heated or unheated metering pump 22 in the direction shown by arrow 20. The temperature of the various components is maintained so that the reagents are in a liquid state. The regulated and constant flow of feedstock exits metering pump 22 through heated or unheated line 24 and is directed into vaporizer unit 26, which vaporizer unit 26 converts the feedstock into a vapor, i.e., a gaseous, aerosol, or atomized stream, of a liquid or solid feedstock. (the vaporizer unit and associated steps are not required if the feedstock 13 held in the container 12 is already in gaseous or other vapor form.) a stream of inert gas 28 may be introduced into the vaporizer 26 from a gas source 30 to direct a stream of vapor out of the vaporizer 26 and into an applicator 32, the applicator 32 including a nozzle facing a substrate, such as a fabric 34, so that a gas stream 36 containing vaporized feedstock is directed onto the fabric 34. The woven or non-woven substrate 34 is moved in the direction of arrows 38 so that the fabric is not heated by the hot gas stream 36 and the volatile material is continuously condensed onto new portions of the fabric. The feed chemicals may be applied to the fabric 34 inside the chamber 40, which helps to keep the vapor away from the plasma region 42 in order to avoid the generation of unwanted chemical radicals and unwanted film deposits on the electrodes 44 and 46. After the feedstock condenses on the surface of the fabric 34, the fabric enters an atmospheric enclosure 48. The housings or chambers 40 and 48 include exhaust devices 50 and 52, respectively. The terms "housing and chamber" are used interchangeably. This does not necessarily mean a completely closed, bounded space, such as in a sealed chamber. The housing or chamber may have an open side or opening in the wall.

Within the housing 48, the fabric 34 passes between electrodes 44 and 46, which electrodes 44 and 46 are part of an atmospheric pressure plasma source that generates the inert gas plasma 42. The plasma can be continuously maintained at 0.25W/cm²And 4W/cm²At a power level in between. For many applications, a concentration of 1W/cm is used²And 2W/cm²The power level in between. The inert gas flow 54 from the source 30 is a plasma gas, and the source 30 may also supply an inert gas to the vaporizer 26. This condensation or deposition of colorant from the feedstock, followed by a plasma-induced color-solidification reaction, may be repeated a selected number of times for producing multiple deposits or coatings of colorant, each time formed prior to the previous formationFor greater fastness and durability. As described above, one or more of the plasma discharges 42 may also employ, for example, a plasma discharge containing fewer added reactive molecules such as H₂、N₂、CF₄Or NH₃To promote the reaction.

Region 56 indicates the portion where no colorant is present (colorant may be present when multiple applicators and plasmas are employed, in which case region 56 will have colorant from an earlier process); region 58 identifies the portion in which the colorant raw chemical is applied; region 60 indicates a plasma polymerization region where the chemicals applied by the vaporizer/applicator are solidified, cured, polymerized, cross-linked, or otherwise combined; and area 62 identifies an area in which the fabric has been treated at least once. Not shown in fig. 1 are: (1) an rf plasma power supply and matching network connected to the electrodes 44 and 46 and used to power the plasma 42 and condition the plasma 42; (2) water cooling (water cooling) for cooling the electrodes 44 and 46 so that the gas temperature of the plasma can be maintained at 70 ℃ or below 70 ℃; (3) a compressed gas regulator for source 30; (4) a drive and rollers for moving the web 34 through the applicator zone into the plasma zone and out of the plasma zone; and (5) pumps in the exhausts 50 and 52 for collecting and recycling the inert gas, all of which are well known to those of ordinary skill in the art. The fabric 34 may be held against one electrode 46 to limit the process to one side thereof. Either electrode may be used for this purpose.

Although applicator chamber or housing 40 and plasma chamber or housing 48 are shown as separate chambers or housings, the features and functions of each may be provided under the same housing. For example, applicator 32 and the plasma source, i.e., electrodes 44, 46 for generating plasma region 42, may be in a single housing. (see, e.g., fig. 2-3, discussed below.) the applicator may operate simultaneously with operation of the electrode that generates the plasma, or the applicator and the electrode may operate sequentially. The applicator may be a separate device in the system that operates independently of the feed inlet for the carrier gas or it may be integrated with the feed inlet for the carrier gas such that the colorant feedstock and carrier gas are in a single, same stream that is introduced into the same housing and subjected to the electric field used to generate the plasma.

In addition to a single set of applicators and plasma sources, a line of applicators/plasma sources may be used to provide multiple deposits or layers of colorant on a single substrate. Similarly, in a single set of applicators/plasma sources, the multilayer deposit or coating may be applied by reversing the movement of the substrate applied after the first operation of the applicator and plasma source back to the applicator and then to the plasma source for the second operation of the applicator and plasma source.

Typical dimensions for the electrodes of the exemplary laboratory plasma device are between 1cm and 13cm wide and 30cm long with a gap between 1mm and 2.5 mm. Typical voltages may be between 120V and 450V (peak-to-peak) at frequencies including 13.56MHz, 27.1MHz and 40.68 MHz.

The subject matter of the present invention is suitable for continuous operation, where the colorant raw material mixture is first applied to a substrate, and then the substrate is deposited with condensed colorant raw material (neat or applied with other chemicals). The treated substrate is then moved into an atmospheric pressure plasma, whereby an inert gas plasma is used to cause the colorant to solidify to the substrate. In addition, the present subject matter is suitable for adding colorant raw materials directly into the plasma cloud via spraying and immediately depositing and curing on the substrate. By applying a sufficiently high power (>0.25W/cm²Usually at 1W/cm²And 2W/cm²In between) it should be possible to process the substrate at a web speed (web speed) of at least e.g. 10-100m/min and using an electrode size (in the direction of web travel) of e.g. 10-200 cm. Operation at atmospheric pressure means that it is not necessary to precondition the fabric to a pre-set moisture level. And alsoIt is not necessary to pulse the plasma so that a greater throughput of the apparatus can be achieved, since the duty cycle of the process is 100%.

Another example of a plasma device that can be used in the method according to the subject matter of the invention is shown in fig. 2-3. In principle, the device allows a rapid flow of active chemical or physical species generated in the plasma region between the electrodes to leave the plasma region and strike the substrate before the active species are deactivated by collisions or energy losses, thereby producing chemical and/or physical changes to the substrate without exposing the substrate to electric fields or charged components present inside the plasma. This effect is achieved by: the "plasma protrusions" are generated from the hollow cathode effect between parallel openings formed in the grounded electrode or RF electrode, and these protrusions are used to assist in carrying the active species from its point of generation further downstream. In the present case, the hollow cathode effect is generated between grounded, liquid-cooled tubular or elliptical electrodes which effectively cool the electrodes and whereby the active species flow after being generated inside the plasma. An advantage of using a circular or elliptical tube to form the ground electrode, as compared to using multiple water-cooled rectangular or square electrodes with similar aspect ratios, is that the elliptical or circular electrode configuration avoids sharp edges that would interfere with and undesirably enhance the discharge near the edges due to the locally enhanced electric field that would result from the relationship E ═ V/r, where r is the radius of curvature of the edges, V is the applied, instantaneous voltage on the electrode, and E is the electric field. The increased electric field may induce arcing. As described above, this downstream processing method also inhibits exposure of the substrate to charged species formed inside the plasma, since such species recombine rapidly after they exit the plasma.

Fig. 2 is a schematic representation of a perspective view of one embodiment of a plasma processing apparatus 110, the plasma processing apparatus 110 shown illustrating an RF electrode 112, the RF electrode 112 having liquid cooled conduits 114a-114d, powered by an RF power supply and RF match network 116 connected to the electrode 112 using copper or other metal tape (not shown in fig. 2), and supported by insulating members 118a-118c, the insulating members 118a-118c may be made of, for example, fiberglass, G10/FR4(McMaster-Carr), phenolic PTFE, glass, or ceramic, whereby a first selected spacing 120 between the RF electrode 112 and a planar ground electrode 122 is maintained, the planar ground electrode 122 being constructed using parallel, grounded, hollow circular or oval tubes 124a-124 d. The power is supplied in a frequency range between about 1MHz and about 100MHz, and the RF matching network is used to adjust the load bias from 50 ohms in the device. The chiller 126 supplies liquid coolant to the cooling conduits 114a-114d and to the hollow tubes 124a-124d adapted for liquid cooling. Rectangular or circular tubes may be used in place of the cooling conduits 114a-114 d. The material to be processed 128 is disposed outside of the plasma proximate the ground electrode 122 and is maintained spaced apart from the ground electrode 122 at a second selected spacing 130. The material 128 may be moved during processing using a suitable moving device 132. Gas inlet tubes 134a-134c supplied through gas supply and manifold 136 provide a suitable gas mixture to gas distribution tubes 138a-138c, nominally 3/8 inches in outer diameter, by way of example, with at least one gas inlet tube 134a for each gas distribution tube 138a to maintain an approximately constant gas pressure across gas distribution tubes 138a-138 c. Gas distribution tubes 138a-138c may be made of, for example, plastic, teflon, or metal. Clearly, the additional inlet tube 134 would be configured to accommodate the wider RF electrode 112. Gas distribution tubes 138a-138c have apertures (not shown in fig. 1) spaced along their length and facing grounded electrode 122 so that gas emerges through tapered channels 140a-140c opening from bottom surface 141 of RF electrode 112. Tapered channels 140a-140c hold gas distribution tubes 138a-138c firmly in place and are recessed from surface 141. The rf electrode 112 is shown as being divided into two opposing portions 112a and 112b so that the channels 114a-114d and 140a-140c can be easily machined and the gas distribution tubes 138a-138c can be installed and used for cleaning and maintenance as needed during operation of the discharge device 110. The three gas distribution tubes 138a-138c shown in FIG. 2 may be separated by a center-to-center spacing of 2.5 inches and recessed from face 141 by 0.125 inches. In another embodiment of the inventive subject matter, if tubes are not employed, O-rings may be used to confine the cooling liquid to the cooling conduits 114a-114c in the opposing portions 112a and 112 b. To prevent the lateral loss of process gas through the apparatus 110, the gas flow is blocked by sealing spaces between the first and last of the ground tubes 124a-124d and the insulating members 118b and 118c so that the gas flow is always directed through the openings between the ground tubes 124a-124d (not shown in FIG. 2).

Fig. 3 is a schematic representation of a side view of plasma processing apparatus 110 herein, showing gas supply tube 134b, water-cooled channels 114b and 114c for RF electrode 112, recessed gas distribution tube 138b, tubular ground electrode 122, and material 128 disposed downstream of the plasma formed in first spacing 120. Also shown are radial holes 142 that allow gas to flow out of gas distribution tube 138b, into tapered channel 140b, and out of surface 141 of RF electrode 112 b. The diameter of the holes 142 may be 0.03 inches. The gap between adjacent grounded electrode tubes 124a-124d may be between about 0.03 inches and 0.12 inches. It is believed that between two plasma discharge devices: one with an electrode gap of about 0.12 inches and the other with an electrode gap of about 0.093 inches, the latter arrangement with more grounded tubes for the same size electrode 22 will give better results for the same flow conditions. The difference may be the result of higher "downstream" gas flow velocities achieved with smaller gaps and better air cooling due to the increased area of the tubes.

As mentioned above, effective cooling of the RF electrode can be achieved by: with square copper or aluminum tubes 114a-114d sandwiched between the top portion 112a and the bottom portion 112b of the RF electrode 112, the RF electrode 112 may also be made of aluminum, and thermostatically controlled cooling water is flowed from a cooler 126, the cooler 126 cooling the RF electrode 112 by conduction. Because neither RF electrode 112 nor ground electrode 122 is covered by a dielectric material, thermal conduction between the electrodes and the gas is greatly enhanced, enabling effective and efficient gas cooling. The grounded electrode 122 includes a series of parallel, equally spaced tubes 124a-124c through which cooling water is also flowed by a cooler 126. The cooling conduits or tubes 114a-114d of the RF electrode 112 and the tubes 124a-124d may well be cooled by other fluids, such as a glycerol-based coolant or, for example, a cooling gas. Air cooling is enhanced over water cooled planar electrodes due to the high surface area provided by tubes 124a-124d of ground electrode 122. For a tube having an outer diameter (o.d.) of 1/4 inches and a gap of open area between the tubes of about 0.09 inches, the increase in surface area on the planar electrodes was a factor of about 2.2. Thus, the downstream gas flow flowing onto the substrate or the substrate can be cooled effectively. When elliptical grounded electrode tubes 124a-124d are used, the short dimension of the tubes is perpendicular to RF electrode 112 and the long dimension is parallel to RF electrode 112.

The flowing gas is used to generate the plasma and to carry active species out of the plasma and onto substrate 128 through the spaces between tubes 144a-144d (fig. 2) of ground electrode 122, which are generated in the plasma discharge between the RF electrode and the ground electrode in space 120. One gas mixture that is effective for this purpose includes between about 85% and about 100% helium gas flowing from gas supply 136 (fig. 2 and 3) into gas inlet tubes 134a-134c and into gas distribution tubes 138a-138c, also shown in fig. 2 and 3 herein. Other gases or vaporized species may be added to the helium gas stream to enhance the formation of reactive species inside the plasma volume. Distribution tubes 138a-138c are fitted with small openings 142 to allow gas to exit the distribution tubes from the plasma-facing side of the electrodes. By placing these distribution tubes within the gaps or channels 140a-140c, respectively, machined into the electrode 112, the distribution tubes remain outside the active area of the plasma, as are the gas outlet openings. The passage does not allow plasma to form immediately adjacent to it because the inter-electrode gap between the RF electrode and the grounded electrode is too large for discharge to occur. The gas distribution tube is arranged away from the discharge in order to prevent arcing events (arcing events) that occur due to the enhanced hollow cathode effect that may occur in the small opening in a similar manner as in microhollow discharges. Three rows of gas distribution tubes have been found to be sufficient to achieve uniform machining of a 2m x 0.3m RF electrode 112 with the longer dimension parallel to distribution tubes 138a-138d, as shown in fig. 3, and wherein the axes of the gas distribution tubes are perpendicular to the movement of material 128.

As described above, gas flow from the plasma is prevented from exiting the plasma region except through the narrow spaces between the tubes. Even with large amounts of electrical power (at about 10W/cm)³And occasionally greater than about 100W/cm³In between) is stored in the plasma, which adds thermal energy to the process gas, but the effective gas cooling effected by the water cooling system and the absence of thermal insulators (e.g., electrical dielectric covers) on the tube and RF electrode keep the gas temperature low. This can be significant, for example, when the present plasma discharge device is used for surface polymerization of thin film monomers, since brief exposure to hot gases will cause condensed monomers on the substrate to rapidly vaporize and escape from the system.

The material 128 can be moved perpendicular to the parallel alignment of the grounded electrode tubes, which provides a uniform surface treatment since all areas of the surface are exposed to the gas flow. The gap between the material and the bottom of the tube can also be controlled and varied. The gap is typically between about 0.5mm and about 10 mm. The large gap enables the device to polymerize monomers applied to thick substrates (e.g., deep-piled carpets), but also has the disadvantage that some of the active chemicals flowing out of the plasma will recombine or be deactivated by other time-dependent means (e.g., by radiation or impact), resulting in slower processing. The small gap between the material and the tube has the advantage of minimal deactivation of the active species, but is also more prone to contaminating the plasma volume between the RF electrode and the ground electrode by mixing any volatile vapors from the material with the process gas. The ability to treat materials that can vent vapors from other processing steps is a significant advantage, as treating such materials using any in situ processing method would result in contamination of the process gases by the vented volatile vapors, or would require such high gas flows as to be cost prohibitive. The close spacing of the tubes also allows the plasma gas to exit at a higher velocity towards the material because the gas flow is directed through a smaller space, which increases the linear velocity of the gas without a concomitant increase in gas consumption and thereby controls costs.

If the substrate or material were to remain stationary in the apparatus, the result would be processed strips, each corresponding to a gap between the grounded electrode tubes 124a-124 d. By moving the substrate through the apparatus in a uniform manner and in a direction perpendicular to the ground electrode, uniform surface finish has been achieved. This provides for continuous processing of the material in an in-line process or a stand-alone batch process. The substrate or material 128 may include, for example, flexible materials such as textiles, carpet, plastic, paper, metal films, and nonwovens, or, for example, rigid materials such as glass, silicon wafers, metal and metal sheets, wood, composites, cardboard, surgical instruments, or skin. The substrate may be a laminate.

The material may be moved using a conveyor belt, a moving table, or by other means of travel. Because the substrate is outside the plasma and the electric field therein, its motion is not complicated. The distance between the substrate and the outlet of plasma-generated species between the grounded electrode tubes 124a-124d is adjusted so that deactivation or decay of the active species does not destroy the chemical reactivity of the gas stream in the downstream region. The placement and movement of the substrate between 0mm to about 10mm from the surface of the grounded electrode tubes 124a-124d may satisfy this condition, depending on the process chemistry.

In summary, in one possible embodiment, stable, non-arcing operation of a plasma requires the following three conditions to be met: (a) a stream of process gas consisting of, for example, between about 85% and about 100% helium; (b) RF excitation of one electrode in a frequency range between about 1MHz and about 100MHz with a bare metal electrode exposed to plasma; and (c) a gap between the RF-driven electrode and the ground electrode of between about 0.5mm and about 3 mm. It is believed that a spacing of about 1.6mm at an RF frequency of about 13.56MHz will yield satisfactory results (and a slightly smaller distance for higher frequencies). In addition, low temperature operation (i.e., between about 0 ℃ and about 100 ℃, or between 10 ℃ and 35 ℃) requires effective cooling of both electrodes using a temperature controlled fluid, such as cooled air, ethylene glycol, or distilled water. The use of conductive fluids such as brine is undesirable due to the corrosive effects of the brine and the possible resulting leakage of the radio frequency power source.

In certain embodiments where the colorant may be applied as a discrete, layered coating, the coating on the textile substrate is between 1nm and 1mm or between 10nm and 100 μm, or between 40nm and 50 μm, or between 0.5 μm and 10 μm, or between 1.0 μm and 5 μm. These ranges are representative and the subject matter of the present disclosure encompasses a wide range of thicknesses and is not intended to be limited to the specific examples given. The 1nm-20nm should satisfy the change of the surface characteristics. However, thicknesses in excess of 20nm may be required to ensure the ability to induce tactile changes in the surface of the fabric.

In certain embodiments, consistent with the teachings of US 8,016,894 for side-specific plasma treatment, one side of the coated textile may be exposed to plasma while the other side of the textile is held in close proximity to a surface unaffected by the plasma species. In this manner, the plasma can selectively modify (e.g., coat) one side of the textile. The side of the fabric facing the impermeable surface is protected from modification by chemicals generated in the plasma. It should be noted that whether the fabric is pressed against an impermeable surface or simply adjacent to a surface, or in the vicinity thereof, by some force will depend on how much of the surface to be protected can be removed or modified without making the difference in properties between the surface and the surface that is intentionally processed or removed insignificant. To process a large number of fabrics, the textile may be moved through the plasma at a selected speed such that the textile spends an effective amount of time in the plasma. In some cases, the plasma treatment may provide functional ligands with additional desirable properties to the surface of the fabric on the plasma-facing side; the coating on the protected side remains substantially coated and may have a different function than the plasma processed side. Thus, the present apparatus and method may be used to achieve a desired dual function fabric.

Raw materials

The dopant (dope) or feedstock solution used in the process according to the inventive subject matter may be a solution or dispersion or other mixture or composition that includes or includes any colorant contemplated herein. In general, the dyes may be provided in a suitably stable and useful form, based on the known chemistry of the dye and the conventionally known solutions for a given dye. In this regard, typically, a dye manufacturer will be able to provide the dye in an appropriate solution or provide the dye with instructions for use. Generally, however, to produce a stock solution of the dye, the dye powder is diluted with water or other solvent. Various known additives necessary for the dye process may be added to the solution. Additives include salts to drive dye migration, anti-caking and anti-dust agents, and the like. In commercial scale applications, the drum (drum) of dye solution is then shipped to the plant for a specific shade/application. At the factory, the solution may be diluted multiple times before the dye reaches the fabric. This dilution will change the shade of the fabric to the desired degree.

In the case of reactive dyes (e.g., for application to cotton or wool), a typical stock solution is about 8% dye, where 70% of it can be salt and the remainder concentrated water or other solvent. The salt helps to drive the dye from the solution into the fiber. The hue of the color is changed by the amount of dye added to the solution.

Typically, the reactive dyes are applied using a cold pad batch process that does not use high temperatures. The fabric was then placed in a steam chamber to drive the reaction. Because the plasma can mimic high temperature reactions, the plasma can replace the vapor chamber process. Furthermore, the salt in the dye solution does not necessarily drive the reaction, since the plasma can activate the dye molecules as well as the fabric surface (drive the reaction). Thus, a stock solution of reactive plasma dye may be a highly concentrated mixture of the dye in a solvent. According to the method of the present invention, the feedstock solution may be produced at a temperature in the range of 0 ℃ to 100 ℃ and/or used in plasma processing for many applications.

In the case of disperse dyes (polyesters), the stock solution may contain certain salts and anti-agglomeration chemicals to keep the dye molecules suspended. In the case of reactive and disperse dyes, the stock solution will be a high concentration of dye and require less other additives (if any) in the stock solution than in conventional dyeing processes. The dye is then atomized into the plasma as a mist.

As used herein, the term "solution" is a broad term that includes not only suitable solutions but also suspensions and colloids. The solvent for the doping solution can be any aqueous solution in which the colorant is soluble or dispersible. Hereinafter, "solvent" is any liquid that can be used to produce dissolved or dispersed particles. Similarly, reference to "dissolving" and similar terms means the act of dissolving or dispersing for the purpose of forming a suitable solution, suspension or colloid.

In light of the foregoing teachings, those skilled in the art will appreciate that various desirable properties or characteristics can be imparted to textile materials as well as other substrates. As used herein, such properties or characteristics include, improved: tactile or hand (e.g., fabric softening), strength, durability, elasticity, flame retardancy, water and/or oil stain repellency, wicking ability, insect-repellency, antistatic properties, fade resistance under sunlight and lighting conditions, and antimicrobial properties that reduce odor, infection, and the formation of mold or mildew. The dyeing and/or treatment may be selectively or preferentially applied to both sides of the fabric substrate, or selectively or preferentially applied to one side or the other. Similarly, the dyeing and treatment may be selectively or preferentially applied to desired regions on the substrate. The selected or preferential treatment may be centered on the same or different chemistry. For example, different zones may be treated with the same composition, but in different amounts for each zone for tailored performance requirements.

The principles described above in connection with any particular example may be combined with the principles described in connection with any one or more of the other examples. Accordingly, this detailed description is not to be construed in a limiting sense, and upon review of this disclosure, those of ordinary skill in the art will understand the wide variety of lending systems (lending systems) and other systems that may be designed using the various concepts described herein. Further, those of ordinary skill in the art will understand that the exemplary embodiments disclosed herein may be applied in a variety of configurations without departing from the disclosed principles.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the disclosed innovations. Various modifications to those embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the disclosure. Thus, the claimed invention is not intended to be limited to the embodiments shown herein, but is to be accorded the full scope consistent with the language claims, wherein reference to an element in the singular, for example, using the article "a" or "an" is not intended to mean "one and only one" unless specifically so stated, but rather "one or more. Furthermore, nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims. The claim element is not to be construed as a "device plus function" claim under united states patent law unless the element is expressly recited using the word "means for.

All patent documents and non-patent documents cited herein are hereby incorporated by reference in their entirety for all purposes.

Claims (22)

1. A method of treating a substrate comprising:

providing a substrate having a generally sheet or planar form or a fiber or yarn form;

providing a colorant to be solidified at a surface of the substrate; and

subjecting the substrate and the colorant to reactive species from a plasma generated by an atmospheric plasma device until the colorant solidifies at the surface of the substrate.

2. The method of claim 1, wherein the substrate comprises a colorant that is deposited on the surface of the substrate prior to subjecting the substrate to reactive species of the plasma, and wherein the reactive species promotes solidification of the colorant at the surface of the substrate after subjecting the substrate with the colorant to the reactive species.

3. The method of claim 1, wherein the colorant is deposited on the substrate after the substrate is placed in the chamber of the plasma apparatus.

4. The method of claim 1, wherein the colorant comprises a dye that is fed into a plasma-generating electric field of a plasma apparatus and the dye and/or surface sites on the substrate are converted into reactive species such that the dye and the substrate are bound together.

5. The method of claim 1, wherein the substrate is placed within the plasma-generating electric field of the plasma device.

6. The method of claim 1, wherein the substrate is placed outside of the plasma-generating electric field of the plasma device but in communication with reactive species generated in the plasma that promote the substrate to fix to the colorant and/or promote the colorant to fix to itself so that the colorant adheres to a coextensive coating on the surface of the lower portion of the substrate.

7. A method of treating a textile with plasma, comprising:

by ink jet printing, supercritical CO₂Dyeing or solution dyeing ofApplying a colorant to a substrate; and

subjecting the textile to reactive species from a plasma generated by an atmospheric plasma device until the colorant solidifies at the surface of the substrate.

8. The method or construct of claims 1, 7, 12, 15 or 16, wherein said colorant is selected from the group consisting of: acid dyes, basic dyes, disperse dyes, direct dyes or dyes for direct dyeing, mordant and chromium dyes, pigments, organic dyes, solvent dyes, azo dyes, sulfur dyes, rayon acetate dyes, nylon dyes, cellulose acetate dyes, and vat dyes.

9. The method or construct of claim 17, 12, 15 or 16, wherein the colorant is selected from the group of: azo dyes, anthraquinone dyes, benzodifuranone dyes, polycyclic aromatic carbonyl dyes, indigoid dyes, polymethine and related dyes, styryl dyes, diarylcarbonium dyes and triarylcarbonium dyes, phthalocyanine dyes, quinophthalone dyes, sulphur dyes, nitro dyes and nitroso dyes and also hybrid dyes.

10. The method or construct of claims 1, 7, 12, 15, or 16, wherein the substrate comprises a textile material.

11. The method of claim 10, wherein the textile material is selected from the group of petroleum-based synthetic fiber textiles consisting of, but not limited to, the following: polyester, nylon, synthetic polyurethane (in the form of synthetic leather), cellulose, and other materials used in footwear, equipment, and apparel.

12. A method of treating a textile, comprising: providing a textile; providing a colorant comprising a monomer to be solidified at a surface of the textile; and subjecting the textile and/or the colorant to plasma conditions sufficient to solidify monomers of the colorant at the surface; and continuing the conditions until the colorant solidifies.

13. The method of claim 12, wherein the conditions are provided by a plasma device configured for atmospheric plasma generation and plasma generated in the device promotes the solidification.

14. The method of claim 1, 7, or 12, further comprising operating a continuous feed assembly coupled to the plasma device to provide for input of a substrate material into a reaction zone of the plasma device.

15. A method of setting a colorant on a substrate, comprising: performing an etching operation on a substrate using a plasma, in particular a plasma generated under atmospheric conditions, to produce a desired surface texture at a surface of the substrate; and depositing a colorant on the surface under plasma conditions or non-plasma conditions; and allowing the colorant to solidify at the surface of the substrate.

16. A construct comprising a substrate material and a colourant solidified at a surface of the substrate, wherein the substrate comprises a textile material having a substantially sheet or planar form and the textile comprises an etched surface treatment layer and a composite of colourant and substrate material in the etched layer.

17. The construct of claim 16, wherein the textile material is selected from the group of petroleum-based synthetic fiber textiles consisting of, but not limited to, the following: polyester, nylon, synthetic polyurethane (in the form of synthetic leather), cellulose, and other materials used in footwear, equipment, and apparel.

18. The construct of claim 16, wherein the colorant comprises a colorant from claim 8 or 9.

19. The construct of claim 16, wherein the substrate is a planar textile material having a surface area of at least 6 square inches.

20. The construct of claim 16, wherein the textile material comprises a roll of textile material of at least any roll size from 10 inches to 72 inches in width and about 1-100 meters in length.

21. An article of apparel or footwear having an outer layer, an intermediate layer, or an inner layer, the article comprising, in whole or in part, the substrate or construct of claim 1, 7, 12, 15, or 16.

22. The subject matter of the present invention as shown and described herein.