Cationic cellulose fibers and methods of making and using the same

Abstract

The present invention relates to cationic cellulosic fibers which can be used to make dyeable fabrics and garments, such as garments having a mixed color effect and / or a denim-like appearance.

Description

[0001] Cross-reference of related applications This application claims the benefit of U.S. Serial No. 63 / 543,611, filed October 11, 2023, and U.S. Serial No. 63 / 567,815, filed March 20, 2024, the disclosures of which are incorporated herein by reference in their entirety.

[0002] Invention Field This invention relates to cationic cellulose fibers, which can be used to prepare dyeable fabrics and garments, such as garments with mixed-color effects and / or denim-like appearance. Background of the Invention Since the invention of indigo-dyed denim technology over a century ago, indigo-dyed denim garments have become a mainstream fashion trend in the apparel industry. Although indigo is classified as a vat dye, it does not actually possess the overall fastness properties known to other vat dyes. Furthermore, indigo has relatively low directness to cotton yarn. For these reasons, indigo denim warp yarns can only be dyed using a multiple-dip process on rope dyeing or beam dyeing systems to achieve the characteristic "ring dyeing effect" of indigo. Ring dyeing occurs when the dye only partially diffuses into the fiber's interior, with most of the dye adhering to the fiber surface, forming a dye layer on the surface, while the dye is almost nonexistent in the core, thus forming a ring-shaped dye appearance visible in cross-section around the fiber. This unique appearance of denim fabric has become a widely accepted iconic look in the denim fashion industry. Subsequently, denim garment production surged globally, gaining a significant market share in the apparel industry.

[0004] While the distressed look of ring-dyed indigo denim is appealing to denim clothing designers, indigo-dyed denim still presents problems. Due to its poor colorfastness to rubbing, it can sometimes leave undesirable blue hues on light-colored garments and fabrics. Furthermore, conventional denim dyeing processes use large amounts of dyes, water, salt, and other environmentally toxic and harmful substances.

[0005] In recent years, the application of cationic reagents to cellulosic fibers has been an active research area. It has been found that the dyeing properties of cellulosic materials are significantly improved when treated with cationic chemicals. Deeper dyeing depths and lower chemical and dye consumption are possible even in reactive dyeing without the use of salts and alkalis. However, unfortunately, the use of cationic reagents often causes problems with fabric treatment uniformity and creates difficulties in controlling dye strikes to produce evenly dyed fabrics. These drawbacks hinder the commercialization of this chemical in many textile applications.

[0006] The most commonly used cationic reagent is Quat 188 manufactured by Dow Chemical Company. ® In the presence of an optimal amount of alkali, the cationic reagent transforms into an active epoxide form, which reacts with the hydroxyl groups of the cellulose material (e.g., cellulose-based yarn fibers) to form covalent bonds, allowing the cationic dye sites of the reagent to be permanently anchored to the cellulose material. These cationic sites alter the dyeing behavior of the cellulose material, enabling it to absorb reactive dyes and other anionic dyes without the aid of additional chemical auxiliaries. However, while the epoxy group can react with the hydroxyl groups in cellulose, it can also hydrolyze in water and become inactive. Due to this instability, alkali and sodium hydroxide must be added to the treatment bath, and the bath solution must be used within 15 minutes, otherwise a tailing effect will occur. The cellulose material then needs to be washed with citric acid to eliminate the undesirable amine odor.

[0007] Another known cationic reagent in the textile industry is EcoFastPure from Dow Chemical Company. ® EcoFast Pure advantageously possesses two epoxy groups, while Quat 188 has only one. Because EcoFast contains more than one epoxy group, even if one epoxy group hydrolyzes during the epoxidation reaction, the reagent remains functional and can react with cellulose materials using the remaining epoxy group. Therefore, EcoFast Pure exhibits a higher fixation rate and a more stable bath than Quat 188. Another advantage of EcoFast Pure is that it does not produce an amine odor. Since cationic reagents themselves have no affinity for cellulose materials, their fixation level on cellulose depends on the concentration of the reagent. This is because activated cationic reagents that only come into direct contact with the cellulose material can react with it, while cationic reagents that do not come into direct contact with cellulose are hydrolyzed and become inactive. Unfortunately, this characteristic of requiring high-liquid-ratio equipment is impractical due to the high cost of the chemicals, making cationic chemistry unsuitable for large-scale commercialization.

[0008] Therefore, there is a need in the art for a commercially viable and environmentally friendly garment dyeing method that can respond to the rapidly changing product demands in the textile industry. The materials and methods described herein address these and other objectives. Invention Overview The present invention described herein provides a cationic cellulose fiber. The cationic cellulose fiber comprises: an outer layer including a plurality of covalently linked cationic portions; and an inner layer substantially free of cationic charge, wherein the thickness ratio of the outer layer to the inner layer is in the range of about 10:1 to about 1:10.

[0010] The present invention further provides a cationic fabric comprising cationic cellulose fibers. The cationic fabric may be a substantially colorless fabric (e.g., gray and / or natural-colored).

[0011] The present invention further provides a garment comprising a cationic fabric. The garment may be a substantially colorless garment and / or a dyed garment (e.g., having a mixed-color effect and / or a denim-like appearance).

[0012] The present invention further provides a method for preparing cationic cellulose fibers, comprising the following steps: immersing untreated cellulose fibers in a cationic treatment solution using a yarn treatment sizing machine to form saturated cellulose fibers, wherein the cationic treatment solution contains a cationic reagent and an alkali; pressing the saturated cellulose fibers through horizontal extrusion rollers to a liquid content of up to approximately 100% of the weight of the untreated cellulose fibers to form pressed cellulose fibers; heating the pressed cellulose fibers to form fixed cationic cellulose fibers; and processing the fixed cationic cellulose fibers to form cationic cellulose fibers.

[0013] The present invention further provides a method for preparing cationic fabric from cationic cellulose fibers by means of the following steps: providing cationic cellulose fibers as warp yarns for weaving; and weaving the cationic cellulose fibers together with untreated weft yarns to obtain cationic fabric.

[0014] The present invention further provides a method for recycling cationic fabric to form regenerated cationic cellulose fibers, comprising the steps of: cutting the cationic fabric to form a plurality of cellulose fiber fragments; and reacting the plurality of cellulose fiber fragments with a cationic treatment solution containing a cationic reagent and an alkali.

[0015] The present invention further provides a method for preparing substantially colorless garments from cationic fabrics by means of the following steps: providing cationic fabrics; and shaping the cationic fabrics into substantially colorless garments.

[0016] The present invention further provides a method for manufacturing a dyed garment from a cationic fabric by means of the following steps: providing a cationic fabric; shaping the cationic fabric into a substantially colorless garment; immersing the substantially colorless garment in a dye bath solution containing water and a wetting agent to form a pretreated garment; and reacting the pretreated garment with an anionic dye, wherein the reaction comprises gradually adding the anionic dye to the dye bath solution containing the pretreated garment, wherein the dye bath solution is substantially free of salt and alkaline content.

[0017] The present invention further provides a method for preparing garments from ring-dyed core yarns by means of the following steps: preparing cationic cellulose fibers, comprising the steps of: treating an outer layer containing a plurality of covalently linked cationic portions, and leaving an inner layer substantially free of cationic charge after the treatment step; weaving the cationic cellulose fibers into an undyed cationic fabric; shaping the undyed cationic fabric into substantially colorless garments and cutting and sewing waste; dyeing the substantially colorless garments with anionic dyes; and reprocessing the cutting and sewing waste into undyed cationic yarns.

[0018] The present invention further provides a cationic cellulose yarn having an outer layer comprising a plurality of covalently linked cationic portions; and an inner layer substantially free of cationic charge, wherein the plurality of covalently linked cationic portions gradually decrease in thickness from the outer layer toward the inner layer.

[0019] The present invention further provides an anionic dyed cellulose yarn comprising a surface layer of yarn that absorbs the maximum proportion of anionic dye; an inner core of yarn that does not absorb anionic dye; and a gradient layer of yarn between the surface layer and the inner core, wherein the gradient layer absorbs a varying amount of anionic dye depending on its distance from the surface layer. Brief description of the attached diagram Figure 1 The present invention displays dyed garments in a range of colors, with a mixed-color effect and a denim-like appearance.

[0021] Figure 2 It is a photographic image of a bundle of dyed yarn fibers of the present invention, each fiber bundle having a ring-dyeing effect.

[0022] Figure 3 A cross-sectional view of the dyed yarn fiber of the present invention is shown, which has a ring-dyeing effect compared with conventional solid dyed yarn fiber. Invention Details This invention relates to the production of colorless fabrics using cationic chemistry, whereby dyeing with anionic dyes (e.g., reactive or direct dyes) in garment form results in a "mixed color effect," for example, providing a unique denim look similar to indigo-dyed denim. Because reactive dyes can be used in the method of this invention, the problem of rubbing fastness in conventional indigo denim dyeing methods is overcome. Furthermore, compared to indigo denim, which can only produce different shades of blue, the garments of this invention can be dyed in a wide variety of color hues (see...). Figure 1 ).

[0024] Unlike treatment in fabric form, the method of this invention allows for cationic treatment of yarns (e.g., warp yarns) to be woven together with untreated yarns into a denim-like fabric, but without color at the fabric stage. The prepared cationic chemical solution has a liquid content of approximately 60-80% of the weight of the treated warp yarns. The method of this invention is considered environmentally friendly because the reactive dyes in the bath are completely depleted, and the small amount of residual chemicals used during dyeing can be easily recycled.

[0025] The warp yarns used are the same as those used in the indigo dyeing method. For example... Figure 2 and Figure 3 As shown, the yarn fibers of the present invention form a "ring-dyeing effect" during dyeing, causing the dye to diffuse only partially into the fiber interior, with most of the dye adhering to the fiber surface, forming a dye layer on the surface, and almost no dye in the core. Thus, a ring-shaped appearance of the dye can be seen in cross-section around the fiber.

[0026] In some embodiments, the present invention particularly provides a cationic cellulose fiber comprising: an outer layer comprising a plurality of covalently linked cationic portions; and an inner layer substantially free of cationic charge, wherein the thickness ratio of the outer layer to the inner layer is in the range of about 10:1 to about 1:10.

[0027] In some embodiments, the cationic cellulose fiber is a yarn fiber. The term "yarn fiber" as used herein should be understood to include all common fiber types, such as filaments of virtually unlimited length as well as shorter fibers. In some embodiments, the yarn fiber of the present invention comprises filaments having a length suitable for the manufacture of textile products.

[0028] In some embodiments, the cationic cellulose fiber is the warp fiber. In other embodiments, the cationic cellulose fiber is the weft fiber. Warp and weft are the two basic components in weaving that transforms yarns into woven fabrics. Vertical warp yarns remain stationary under tension on the loom, while horizontal weft yarns insert above and below the warp yarns.

[0029] In some embodiments, the cellulose fibers of the present invention are in the form of raw slivers and / or cooked slivers.

[0030] In some implementations, the cationic cellulose fibers are in the form of strips.

[0031] In some implementations, the cationic cellulose fibers are in strip form, such as spun strips.

[0032] Converting raw cotton bales into finished slivers involves passing the opened and cleaned cotton fibers through a carding machine, which removes short fibers from the raw cotton to form a sliver. These fibers are then passed through a drawing frame to create a stronger sliver with better fiber alignment, resulting in cleaner subsequent processing and reduced lint.

[0033] In some embodiments, the cationic cellulose fibers of the present invention contain cationic portions in the outer layer and / or surface of the fibers.

[0034] In some embodiments, the cationic moiety is a functional group derived from a quaternary ammonium salt. This cationic moiety can be derived, for example, from compounds such as N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride (Quat 188; manufactured by Dow Chemicals Inc.) and / or 1-propylammonium-N,N'-(oxydi-2,1-ethylenediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl]dichloride (EcoFast Pure, CAS# 96320-92-2; manufactured by Dow Chemicals Inc.), with the structures shown below.

[0035] In some embodiments, the cationic cellulose fibers of the present invention are derived from N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride.

[0036] In some embodiments, the cationic moiety is derived from 1-propanenyl-N,N'-(oxydi-2,1-ethylenediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl]dichloride.

[0037] In some embodiments, the ratio of the outer layer to the inner layer of the cationic cellulose fibers is in the range of approximately 10:1 to approximately 1:10. In some embodiments, the ratio of the outer layer to the inner layer is approximately 1:1.

[0038] In some embodiments, the inner layer of the cationic cellulose fiber is substantially free of cationic charge. In some embodiments, there is no cationic charge in the inner layer.

[0039] In some implementations, the multiple covalently linked cationic portions gradually decrease in thickness from the outer layer to the inner layer.

[0040] In some embodiments, cationic cellulose fibers are prepared by a method comprising the following steps: Untreated cellulose fibers are immersed in a cationic treatment solution using a yarn treatment sizing machine to form saturated cellulose fibers, wherein the cationic treatment solution contains a cationic reagent and an alkali. Saturated cellulose fibers are rolled using horizontal extrusion rollers to a liquid content of up to approximately 100% of the weight of untreated cellulose fibers to form rolled cellulose fibers. Heat-impregnated cellulose fibers to form fixed cationic cellulose fibers; and Processing fixed cationic cellulose fibers to form cationic cellulose fibers.

[0041] Untreated cellulose fibers can be synthetic fibers and / or blends of synthetic and natural fibers that can be separated from natural sources. In some embodiments, the untreated cellulose fibers are separated from cotton, flax, hemp, jute, and / or ramie.

[0042] In some embodiments, the untreated cellulose fibers are separated from cotton. In some embodiments, the untreated cellulose fibers are separated from hemp.

[0043] In some embodiments, the cation treatment solution is any solution containing a cationic reagent that can at least partially react with cellulose fibers and introduce a positive charge by, for example, covalently attaching a positively charged chemical portion to the surface of the cellulose fibers.

[0044] In some embodiments, the cationic reagent is a quaternary ammonium salt, such as, for example, N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride and / or 1-propanediol-N,N'-(oxydi-2,1-ethylenediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl]dichloride.

[0045] In some embodiments, the cationic reagent is N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride (Quat 188).

[0046] In some embodiments, the cation reagent is 1-propanenyl-N,N'-(oxydi-2,1-ethylenediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl]dichloride (EcoFast Pure).

[0047] In some embodiments, the cationic treatment solution further comprises a base. Without being bound by any particular theory of the invention, it is believed that when the cationic reagent reacts in the presence of an optimal amount of base, it transforms into an active epoxide form that reacts with the hydroxyl groups of the cellulose material, thereby forming covalent bonds that allow the cationic functional groups to be permanently anchored to the cellulose material.

[0048] In some embodiments, the alkali is an alkaline ionic salt, oxide, or hydroxide of an alkali metal.

[0049] In some embodiments, the base is sodium hydroxide.

[0050] In some embodiments, the ratio of cationic reagent to base in the cationic treatment solution is in the range of about 10:1 to about 1:10.

[0051] In some embodiments, the ratio of cationic reagent to base in the cationic treatment solution is in the range of about 10:1 to about 1:1.

[0052] In some implementations, the ratio of cationic reagent to base in the cationic treatment solution is approximately 2:1.

[0053] In some embodiments, the ratio of the cationic treatment solution to the untreated cellulose fibers is approximately 10:1 to approximately 1:10.

[0054] In some implementations, the ratio of cationic treatment solution to untreated cellulose fibers is approximately 2:1.

[0055] In some implementations, the ratio of cationic treatment solution to untreated cellulose fibers is approximately 1:1.

[0056] In some embodiments, the cation treatment solution may further comprise a wetting agent. The wetting agent may include any agent, for example, that reduces the surface area of ​​water. The wetting agent may include, for example, a fatty alcohol ethoxylate, such as AlbaflowConti. ® .

[0057] In some embodiments, the cationic treatment solution may further comprise an antifoaming agent. The antifoaming agent may include, for example, any agent having "antifoaming" properties and / or causing complete or partial prevention of foam formation.

[0058] In some embodiments, the cationic treatment is followed by a step of forming the saturated cellulose fibers by rolling them with horizontal extrusion rollers to a liquid content of about 40% to about 90% (or about 60% to about 80%) of the weight of the untreated cellulose fibers.

[0059] In some embodiments, the cationic treatment is followed by a step of forming the saturated cellulose fibers by rolling them with a liquid content of up to about 100% (or about 40%, about 50%, about 60%, about 70%, about 80%, or about 90%, or about 60% to about 80%) of the weight of the untreated cellulose fibers using horizontal extrusion rollers.

[0060] In some embodiments, the impregnated cellulose fibers are then heated to form fixed cellulose fibers.

[0061] In some embodiments, the impregnated cellulose fibers are heated by conveying them through a heating device selected from a heating bath, a steam chamber, a dry can column, and a hot air chamber.

[0062] In some embodiments, the method further includes drying the impregnated cellulose fibers in an infrared pre-dryer prior to the heating step.

[0063] In some embodiments, the heating step that forms the fixed cationic cellulose fibers is followed by further processing. Processing may include, for example, neutralizing, rinsing, and / or drying the fixed cationic cellulose fibers. Processing may further include sizing the cationic fibers and winding them onto a warp beam for weaving.

[0064] In some embodiments, the present invention further provides cationic fabrics comprising cationic cellulose fibers. The cationic fabrics may be substantially colorless. As used herein, the term "substantially colorless" means that the fabric contains virtually no color and / or only mild or neutral tints (e.g., gray and / or natural colors).

[0065] In some implementations, the cationic fabric is essentially colorless.

[0066] In some implementations, the cationic fabric is gray.

[0067] In some implementations, the cationic fabric is natural-colored.

[0068] In some embodiments, cationic fabrics can be prepared by a method including the following steps: Provide cationic cellulose fibers as warp yarns for weaving; and Cationic cellulose fibers are woven together with untreated weft yarns to obtain cationic fabrics.

[0069] In some embodiments, the invention further provides garments comprising cationic fabrics. The garments may be substantially colorless (e.g., gray or natural-colored), or they may be dyed garments.

[0070] In some implementations, the garments are essentially colorless.

[0071] In some implementations, the garment is gray.

[0072] In some implementation schemes, the garments are natural-colored.

[0073] In some implementations, the garment is a dyed garment.

[0074] In some implementations, the garment features a mixed-color effect. As used herein, the term "mixed-color" refers to the distinctive two-tone color effects and textured patterns typically found in conventionally manufactured jeans.

[0075] In some implementations, the garment has a denim-like appearance; for example, based on the appearance of the garment, it is substantially indistinguishable from and / or cannot be distinguished from actual denim.

[0076] In some embodiments, the present invention provides a substantially colorless garment that can be prepared by the following method: Provide cationic fabrics; and The cationic fabric is shaped into essentially colorless garments.

[0077] Forming may include, for example, cutting and / or sewing cationic fabrics into essentially colorless garments.

[0078] In some embodiments, the present invention provides a dyed garment prepared by a method comprising the following steps: Provide cationic fabrics; Cationic fabrics are shaped into essentially colorless garments; The essentially colorless garments are immersed in a dye bath solution containing water and a wetting agent to form pretreated garments; and The pretreated garment is reacted with anionic dye, wherein the reaction comprises gradually adding the anionic dye to a dye bath solution containing the pretreated garment, wherein the dye bath solution is substantially free of salt and alkaline contents.

[0079] The applicant was surprised to find that this unique combination of steps resulted in minimal chemicals and virtually no unabsorbed dye residue in the bath. Both the dye bath and the rinsing bath can be recycled for subsequent dyeing batches; moreover, wastewater discharge is minimal and no landfill is required.

[0080] In some embodiments, forming includes cutting and / or sewing cationic fabrics into substantially colorless garments.

[0081] In some implementations, the substantially colorless garment is constructed such that the outer portion of the garment faces outward prior to the reaction step.

[0082] In some embodiments, colorless garments are immersed in a dye bath solution containing water and a wetting agent to form pretreated garments. The wetting agent can be any agent that improves the spreading and penetrating properties of a liquid, for example, by reducing the surface tension of the liquid. In some embodiments, the wetting agent is a fatty alcohol ethoxylate compound, such as Albaflow Conti. ® .

[0083] In some embodiments, the concentration of the wetting agent is from about 0.1 g / L to about 10 g / L.

[0084] In some implementations, the concentration of the wetting agent is approximately 0.5 g / L.

[0085] In some embodiments, the pretreated garment is reacted with anionic dye, wherein the reaction involves gradually adding the anionic dye to a dye bath solution containing the pretreated garment, wherein the dye bath solution is substantially free of salt and alkaline contents.

[0086] In some implementations, the anionic dye is a direct dye, a reactive dye, or an acid dye.

[0087] In some embodiments, the anionic dyes are direct dyes. Direct dyes are high molecular weight, water-soluble anionic dyes used for dyeing cellulosic materials. They are selected based on the criterion that their lightfastness is unaffected by the presence of the cationic reagent. Those with more SO3Na groups may be useful for certain advantageous properties, such as good dye uptake, wash fastness, and deep earth-tone dyeing. In some embodiments, dye fixation after dyeing is not required because the cationic sites will also act as dye fixatives to bind the solubilizing groups. Due to their high affinity for cotton fibers, direct dyes can also dye untreated cotton weft yarns to impart a different dyeing effect to garments, where treated warp yarns appear darker than weft yarns. However, the rubbing fastness and wash fastness properties of this type of dye are slightly inferior to those of reactive dyes in some cases.

[0088] In some embodiments, the anionic dye contains an SO3Na group.

[0089] In some embodiments, the anionic dyes are acid dyes. Acid dyes are primarily used for dyeing animal fibers and nylon. Due to the anionic nature of these dyes in water, they can be used, for example, to dye the garments of the present invention to bright hues, but will not dye or stain the cotton weft yarns of garments not treated with cationic reagents. In a stripping bath, in the presence of a mild alkaline solution containing as little as 0.5 g / L of soda ash, the dye can be readily stripped from the garment.

[0090] In some embodiments, the anionic dye is a reducing sulfur dye. Reducing sulfur dyes are water-insoluble dyes that must be reduced to their soluble anionic form using an alkali and a reducing agent before dyeing. Like direct dyes, reducing sulfur dyes can dye both cationic-treated and untreated yarns. The garments of this invention can be dyed using the same dyeing procedures as conventional sulfur dye applications.

[0091] In some embodiments, the anionic dye is a reactive dye. Reactive dyes have a wide color gamut, ranging from bright hues to navy and deep black. In summary, garments of the present invention dyed with reactive dyes exhibit outstanding wash fastness and rubbing fastness. Bifunctional reactive dyes for exhaustion applications can be used to dye garments of the present invention. Bifunctional means that the dye has two identical functional groups or two different functional groups. These high molecular weight reactive dyes have high directness to cotton fibers. The reactive dye series from Everlight Inc., called the Everzol ED (Exhaustion) series, has bright hues and high tinting strength. A dyeing strength of 1-1.5% OWM can produce deep hues, and the dye bath is completely exhausted even without the use of salts and alkalis in conventional reactive dyeing. This is because the reactive dye is absorbed by only 25% of the entire cationicly treated garment of the present invention. Since there are no salts and alkalis as dyeing auxiliaries, the remaining untreated portion of the garment remains undyed.

[0092] In some implementations, the reactive dye is a bifunctional reactive dye.

[0093] In some implementations, the reactive dye is a high molecular weight reactive dye.

[0094] In some implementations, the reactive dye is an Everzol ED dye.

[0095] In some implementations, the reactive dye is vinyl sulfone (Remazol). ® )dye.

[0096] In some embodiments, the anionic dye is a bifunctional reactive dye containing at least one vinyl sulfone moiety.

[0097] In some implementations, the weight ratio of the substantially colorless garment to the dye bath solution is in the range of approximately 1:4 to approximately 1:50.

[0098] In some implementations, the dye bath solution is essentially free of sodium chloride and sodium sulfate.

[0099] In some embodiments, the dye bath solution further comprises a dispersant and / or a leveling agent. The dispersant and / or leveling agent may include, for example, lignin sulfonate.

[0100] In some embodiments, the reaction steps are carried out at ambient room temperature. In other embodiments, the reaction steps are carried out at a temperature ranging from about 65°C to about 90°C, or at a temperature of 85°C.

[0101] In some implementations, the reaction step lasts from about 5 minutes to about 30 minutes, or about 15 minutes.

[0102] In some embodiments, the reaction steps include gradually adding anionic dye to the dye bath solution and then reacting for about 10 minutes, then increasing the dye bath temperature to 85°C at a rate of 1°C / min and then reacting for about 15 minutes.

[0103] In some implementations, a replenishment step follows the reaction step, in which the dye bath is drained after the reaction step and then replenished with a second dye bath solution containing water, wetting agent and anionic dye.

[0104] In some embodiments, the method for preparing dyed garments further includes a cold rinsing step after the reaction step, in which the dye bath solution is drained and the drained garment is cold-rinsed. The duration of the cold rinsing step can be, for example, from about 5 minutes to about 20 minutes, or about 10 minutes.

[0105] In some implementations, the colorless garment is pre-shrinked prior to the reaction step.

[0106] In some embodiments, the present invention further provides a method for preparing the cationic cellulose fibers of the present invention by reacting untreated cellulose fibers with a cationic treatment solution containing a cationic reagent and a base.

[0107] In some implementations, the untreated cellulose fibers are separated from cotton, flax, hemp, jute, and / or ramie.

[0108] In some implementations, untreated cellulose fibers are separated from cotton.

[0109] In some implementations, untreated cellulose fibers are isolated from cannabis.

[0110] In some implementations, the untreated cellulose fibers are yarn fibers.

[0111] In some implementations, the yarn fiber is one of the warp or weft fibers.

[0112] In some implementations, the untreated cellulose fibers are either in raw or cooked form.

[0113] In some implementations, the untreated cellulose fibers are in the form of raw strips.

[0114] In some implementations, the untreated cellulose fibers are in the form of mature strips.

[0115] In some implementations, the cationic reagent is a quaternary ammonium salt.

[0116] In some embodiments, the cation reagent is selected from N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride and 1-propanediol-N,N'-(oxydi-2,1-ethylenediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl]dichloride.

[0117] In some embodiments, the cationic reagent is N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride.

[0118] In some embodiments, the cation reagent is 1-propanenyl-N,N'-(oxydi-2,1-ethylenediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl]dichloride.

[0119] In some embodiments, the base is sodium hydroxide.

[0120] In some embodiments, the ratio of the cation to the base in the reaction step is in the range of about 10:1 to about 1:10, or in the range of about 10:1 to about 1:1, or about 2:1.

[0121] In some embodiments, the ratio of the cationic treatment solution to the untreated cellulose fibers is about 10:1 to about 1:10, or about 2:1, or about 1:1.

[0122] In some embodiments, the cation treatment solution further includes a wetting agent.

[0123] Wetting agents may include, for example, fatty alcohol ethoxylate compounds (Albaflow Conti) ® ).

[0124] The cationic treatment solution may further contain an antifoaming agent.

[0125] In some implementations, the duration of the reaction step is less than about 15 minutes, or less than about 10 minutes, or about 10-15 minutes.

[0126] The reaction step can be carried out with or without heating. In some embodiments, the reaction step is carried out without heating. In other embodiments, the reaction step is carried out at a temperature of about 50°C to about 100°C, or about 85°C. In some embodiments, the reaction step is carried out by heating the reaction to its boiling point.

[0127] In some implementations, the reaction steps are carried out in textile machinery.

[0128] In some implementations, the heat source for the reaction step comes from steam passing through heating coils in the textile machinery.

[0129] In some implementations, the heat source for the reaction step comes from the stainless steel rollers of the textile machinery.

[0130] In some implementations, the heat source comes from a hot air chamber.

[0131] In some implementations, the heat source for the reaction step comes from the steam chamber of the textile machinery.

[0132] In some embodiments, the reaction steps are carried out in textile machinery without heating and include the step of impregnating the cellulose fibers with a treatment solution containing a cationic reagent and an alkali. Impregnation can be carried out in an airless environment for 18-24 hours.

[0133] In some embodiments, the method further includes a step of separating crude cationic cellulose fibers after the reaction step. The crude cationic cellulose fibers can be washed and neutralized with an acid (e.g., citric acid) to obtain purified cationic cellulose fibers. In some embodiments, washing and neutralization eliminate undesirable amine odors.

[0134] In some implementations, untreated cellulose fibers are treated with a cationic treatment solution using a yarn treatment sizing machine. The yarn treatment sizing machine may be equipped with a heating device to promote fixation.

[0135] In some implementations, untreated cellulose fibers are treated with a cationic treatment solution in a package dyeing machine.

[0136] In some embodiments, the present invention provides a method for preparing cationic cellulose fibers through the following steps: Untreated cellulose fibers are immersed in a cationic treatment solution to form saturated cellulose fibers using a yarn treatment sizing machine, wherein the cationic treatment solution contains a cationic reagent and an alkali; Saturated cellulose fibers are rolled using horizontal extrusion rollers to a liquid content of up to approximately 100% of the weight of untreated cellulose fibers to form rolled cellulose fibers. The cellulose fibers are heated and impregnated to form fixed cationic cellulose fibers; The fixed cationic cellulose fibers are processed to obtain cationic cellulose fibers.

[0137] In some embodiments, the impregnated cellulose fibers are heated by conveying them through a heating device selected from a heating bath, a steam chamber, a drying cylinder, and a hot air chamber.

[0138] In some embodiments, the method further includes drying the impregnated cellulose fibers in an infrared pre-dryer prior to the heating step.

[0139] In some embodiments, the method includes processing steps that include, for example, neutralizing, rinsing, and drying the fixed cationic cellulose fibers.

[0140] In some embodiments, the method further includes sizing cationic fibers and winding them onto a warp beam for weaving.

[0141] In some embodiments, the present invention further provides a method for preparing cationic fabrics from cationic cellulose fibers through the following steps: Provide cationic cellulose fibers as warp yarns for weaving; and Cationic cellulose fibers are woven together with untreated weft yarns to obtain cationic fabrics.

[0142] In some embodiments, the cationic fabric is substantially colorless. In other embodiments, the cationic fabric is gray and / or natural-colored.

[0143] In some embodiments, the method further includes a pre-shrinking step of the cationic fabric. The cationic fabric may be pre-shrinked to, for example, a residual shrinkage rate of -3%.

[0144] In some embodiments, the present invention further provides a method for recycling cationic fabrics to form regenerated cationic cellulose fibers through the following steps: Cutting cationic fabrics to form multiple cellulose fiber fragments; and Multiple cellulose fiber fragments are reacted with a cationic treatment solution containing a cationic reagent and a base.

[0145] In some embodiments, the present invention provides regenerated cationic cellulose fibers, wherein the regenerated cationic cellulose fibers are capable of forming ring-dyed core yarns when treated with anionic dyes, wherein the ring-dyed core has a speckled appearance.

[0146] In some embodiments, the present invention further provides a method for preparing substantially colorless garments from cationic fabrics by means of the following steps: Provide cationic fabrics; and The cationic fabric is shaped into essentially colorless garments.

[0147] In some embodiments, forming includes cutting and / or sewing cationic fabrics into substantially colorless garments.

[0148] In some implementations, essentially colorless garments are gray and / or natural-colored.

[0149] In some embodiments, the present invention provides a method for preparing dyed garments from cationic fabrics through the following steps: Provide cationic fabrics; Cationic fabrics are shaped into essentially colorless garments; The essentially colorless garments are immersed in a dye bath solution containing water and a wetting agent to form pretreated garments; and The pretreated garment is reacted with anionic dye, wherein the reaction comprises gradually adding the anionic dye to a dye bath solution containing the pretreated garment, wherein the dye bath solution is substantially free of salt and alkaline contents.

[0150] In some embodiments, forming includes cutting and / or sewing cationic fabrics into substantially colorless garments.

[0151] In some implementations, the substantially colorless garment is constructed such that the outer portion of the garment faces outward prior to the reaction step.

[0152] In some implementations, the wetting agent is a fatty alcohol ethoxylate compound (Albaflow Conti). ® The concentration of the wetting agent can be, for example, from about 0.1 g / L to about 10 g / L, or about 0.5 g / L.

[0153] In some implementations, the anionic dye used in this method is a direct dye, a reactive dye, or an acid dye.

[0154] In some embodiments, the anionic dye contains an SO3Na group.

[0155] In some implementations, the anionic dye is an acid dye.

[0156] In some implementations, the anionic dye is a direct dye.

[0157] In some implementations, the anionic dye is a reduced sulfur dye.

[0158] In some implementations, the anionic dye is a reactive dye.

[0159] In some implementations, the reactive dye is a bifunctional reactive dye.

[0160] In some implementations, the reactive dye is a high molecular weight reactive dye.

[0161] In some implementations, the reactive dye is a bifunctional dye.

[0162] In some implementations, the reactive dye is a vinyl sulfone dye.

[0163] In some embodiments, the anionic dye is a bifunctional dye containing at least one vinyl sulfone group.

[0164] In some implementations, the weight ratio of the substantially colorless garment to the dye bath solution is in the range of approximately 1:4 to approximately 1:50.

[0165] In some implementations, the dye bath solution used in this method is substantially free of sodium chloride and sodium sulfate.

[0166] In some embodiments, the dye bath solution further comprises a dispersant and / or a leveling agent.

[0167] In some embodiments, the dispersant and / or leveling agent is lignin sulfonate.

[0168] In some implementations, the reaction steps are carried out at ambient room temperature.

[0169] In some embodiments, the reaction steps are carried out at a temperature ranging from about 65°C to about 90°C, or at a temperature of about 85°C.

[0170] In some implementations, the reaction step lasts from about 5 minutes to about 30 minutes, or about 15 minutes.

[0171] In some embodiments, the reaction steps include gradually adding anionic dye to the dye bath solution and then reacting for about 10 minutes, then increasing the dye bath temperature to 85°C at a rate of 1°C / min and then reacting for about 15 minutes.

[0172] In some embodiments, the method further includes a replenishment step, wherein the dye bath is drained after the reaction step and subsequently replenished with a second dye bath solution containing water, a wetting agent, and anionic dye.

[0173] In some embodiments, the method further includes a cold rinsing step after the reaction step, in which the dye bath solution is drained and the drained garment is cold-rinsed. The duration of the cold rinsing step can be, for example, from about 5 minutes to about 20 minutes, or about 10 minutes.

[0174] In some implementations, the colorless garment is pre-shrinked prior to the reaction step.

[0175] In some implementations, the dyed garments have a mixed-color effect and / or a denim-like appearance.

[0176] In some embodiments, the present invention provides a method for producing garments from ring-dyed core yarn through the following steps: Cationic cellulose fibers were prepared using the following steps: The outer layer, containing multiple covalently linked cation portions, is treated; and The processing steps leave an inner layer that is essentially free of cationic charge; Cationic cellulose fibers are woven into undyed cationic fabrics; Undyed cationic fabrics are shaped into essentially colorless garments and cutting and sewing waste; Dyeing essentially colorless garments with anionic dyes; and Cutting and sewing waste is reprocessed into undyed cationic yarn.

[0177] In some implementations, undyed cationic yarns are woven into undyed cationic fabrics.

[0178] In some implementations, the reprocessing steps include cutting and grinding the sewing waste.

[0179] In some embodiments, the present invention further provides a cationic cellulose yarn comprising: The outer layer contains multiple covalently linked cation moieties; and The inner layer is essentially free of cationic charges. The thickness of the multiple covalently linked cations gradually decreases from the outer layer to the inner layer.

[0180] In some embodiments, the present invention further provides an anion-dyed cellulose yarn having The surface layer of yarn that absorbs the largest proportion of anionic dyes; The inner core of yarns that do not absorb anionic dyes; and The yarn has a gradient layer between the surface layer and the inner core, wherein the gradient layer absorbs varying amounts of anionic dye depending on its distance from the surface layer.

[0181] In some implementations, the amount of anionic dye absorbed by the gradient layer is at its maximum near the surface layer and at its minimum near the core.

[0182] As is known in industry and the prior art, approximately 99% of fabrics are produced by weaving dyed yarns or dyeing entire rolls of fabric. Garments are then cut and sewn from the dyed fabric to form finished garments. In contrast to the prior art, one embodiment of the present invention uses yarns that can be treated using the methods described above. The treated yarns can then be woven together with other treated yarns or with untreated yarns to form a fabric. The fabric in this embodiment is colorless or grange. This fabric can be cut and sewn into undyed finished garments, including zippers, buttons, pocket linens, and labels. The undyed finished garments can then be dyed using the methods described above, with only the treated yarns receiving the dye. All other features of the garment remain undyed, including the untreated yarns, zippers, buttons, pocket linens, and labels. Cutting and sewing waste from producing colorless finished garments can be recycled and re-treated into treated yarn to form another colorless finished garment. This example enables the dyeing of cut and sewn garments at the garment level, allowing for better control of inventory and almost "on-demand" dynamic delivery of any of the virtually unlimited colorpallets.

[0183] A contrasting example from existing technology is the production of denim. The yarn is dyed indigo, which has all the aforementioned drawbacks. It is then woven together with undyed yarn, where the indigo yarn is the warp and the undyed yarn is the weft. After the denim fabric is made, "blue jeans" are produced by adding zippers, buttons, pocket linings, and labels during the cutting and sewing process. Cutting and sewing waste from this process can only be dyed blue again because the recycled fibers still contain blue dye. Furthermore, the entire garment cannot be made colorless because, in any process of dyeing the finished garment, the undyed yarn and the zippers, buttons, pocket linings, and labels will all be dyed indigo.

[0184] In some embodiments, the present invention provides a method for dyeing garment accessories other than garments, whereby garment accessories such as sewing thread and zippers are treated with a cationic reagent solution described herein, such that they match the color of the dyed garment after the dyeing step. Garment accessories can be dyed using the method described herein, for example, using mercerized cotton as the thread for garment accessories. The garment accessories are then treated with a cationic reagent, followed by optional rinsing and neutralization steps.

[0185] In some embodiments, the present invention produces garment-dyed warp yarns with ring-dyed cores, replacing indigo or sulfur yarns in the warp yarns of denim fabrics. In some embodiments, the present invention utilizes a custom-designed yarn processing machine that subsequently manufactures yarns (e.g., warp yarns) with ring-dyed cores. The processing machine comprises multiple components (e.g., separate electronic and / or steel components) and processes. The yarns treated with this machine undergo a transformation that alters their yarn structure, making them suitable for producing garment-dyed clothing and footwear. Specifically, the fabric is woven from the treated yarns and subsequently sewn into an undyed garment. This garment can then be dyed to an unlimited range of warp colors with ring-dyed cores. Unlike conventionally manufactured blue jeans using indigo dyes and / or sulfur dyes (which require large amounts of water and toxic chemicals), the yarns of the present invention eliminate the need for dyeing yarns with indigo or sulfur dyes, reduce water consumption by 85% or more, and eliminate the use of toxic chemicals. The present invention provides a method for dyeing warp yarns into unlimited garment dyeing colors, having a ring-dyed core that fades and wears like indigo yarn or sulfur dye-dyed yarn.

[0186] In some embodiments, the present invention provides a keratin fiber capable of forming a ring-dyed core yarn when treated with anionic dyes. The anionicly dyed keratin yarn may comprise: The surface layer of yarn that absorbs the maximum proportion of anionic dyes; The inner core of yarns that do not absorb anionic dyes; and The yarn has a gradient layer between the surface layer and the inner core, wherein the gradient layer absorbs varying amounts of anionic dye depending on its distance from the surface layer.

[0187] In some implementations, the amount of anionic dye absorbed by the gradient layer is at its maximum near the surface layer and at its minimum near the core.

[0188] In some implementations, the keratin fibers contain keratin derived from the hair, nails, feathers, horns, or claws of mammals.

[0189] In some implementations, keratin is derived from wool.

[0190] In some embodiments, the present invention provides a keratin fabric comprising keratin fibers. The keratin fibers may be substantially colorless and / or gray or natural-colored.

[0191] In some embodiments, keratin fabrics are prepared by a method comprising the following steps: Provide keratin fibers as warp yarns for weaving; and Keratin fibers are woven together with untreated weft yarns to obtain keratin fabrics.

[0192] In some embodiments, the present invention provides a garment comprising a keratin fabric. The garment may be substantially colorless and / or gray or natural-colored.

[0193] In some implementations, keratin-based garments are dyed garments, such as garments with a mixed-color effect and / or a denim-like appearance.

[0194] In some implementations, the essentially colorless garment is prepared by a method comprising the following steps: Provide keratin fabrics; and Shape keratin fabric into substantially colorless garments. Shaping may include cutting and / or sewing keratin fabric into substantially colorless garments.

[0195] In some embodiments, the present invention provides a dyed garment prepared by a method comprising the following steps: Provide keratin fabrics; Shape keratin fabrics into essentially colorless garments; The essentially colorless garments are immersed in a dye bath solution containing water and a wetting agent to form pretreated garments; and The pretreated garment is reacted with anionic dye, wherein the reaction comprises gradually adding the anionic dye to a dye bath solution containing the pretreated garment, wherein the dye bath solution is substantially free of salt and alkaline contents.

[0196] In some embodiments, the present invention provides a fabric comprising: At least one of treated cellulose fibers and treated keratin fibers, which are treated to accept anionic dyes and form ring-dyed core yarns; At least one of untreated cellulose fibers and untreated keratin fibers; Among them, ring-dyed core yarn is one of the warp or weft yarns of the fabric; and At least one of the untreated cellulose fibers and untreated keratin fibers is another type of warp or weft yarn from ring-dyed core yarn.

[0197] All publications, patents, and patent applications cited in this article (including all cited technologies and references) are incorporated herein in their entirety for all purposes.

[0198] While many forms of the invention disclosed herein constitute the presently preferred embodiments, many other forms are possible, and further details of the preferred and other possible embodiments should not be construed as limiting. It should be understood that the terminology used herein is descriptive rather than limiting, and various changes and many equivalents may be made without departing from the spirit or scope of the claimed invention.

[0199] Aspects of the present invention The present invention further includes the following aspects and embodiments: 1. A cationic cellulose fiber comprising: The outer layer contains multiple covalently linked cation moieties; and The inner layer is essentially free of cationic charges. The thickness ratio of the outer layer to the inner layer is in the range of approximately 10:1 to approximately 1:10.

[0200] 2. The cationic cellulose fiber in aspect 1 is a yarn fiber.

[0201] 3. The cationic cellulose fiber of aspect 2, which is one of the warp and weft fibers.

[0202] 4. The cationic cellulose fiber of aspect 2, which is either in the form of raw sliver or cooked sliver.

[0203] 5. The cationic cellulose fiber of aspect 2 is in the form of a strip.

[0204] 6. The cationic cellulose fiber of aspect 2 is in the form of molten sliver.

[0205] 7. Aspect 1: cationic cellulose fibers, wherein the cationic portion is derived from quaternary ammonium salts.

[0206] 8. The cationic cellulose fiber of aspect 1, wherein the cationic portion is derived from N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride and / or 1-propanediyl-N,N'-(oxydi-2,1-ethylenediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl]dichloride.

[0207] 9. The cationic cellulose fiber of aspect 1, wherein the cationic portion is derived from N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride.

[0208] 10. Aspect 1 of cationic cellulose fibers, wherein the cationic portion is derived from 1-propanenyl-N,N'-(oxydi-2,1-ethylenediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl]dichloride.

[0209] 11. The cationic cellulose fiber of aspect 1, which is prepared by a method comprising the following steps: Untreated cellulose fibers are immersed in a cationic treatment solution using a yarn treatment sizing machine to form saturated cellulose fibers, wherein the cationic treatment solution contains a cationic reagent and an alkali. Saturated cellulose fibers are rolled using horizontal extrusion rollers to a liquid content of up to approximately 100% of the weight of untreated cellulose fibers to form rolled cellulose fibers. Heat-impregnated cellulose fibers to form fixed cationic cellulose fibers; and Processing fixed cationic cellulose fibers to form cationic cellulose fibers.

[0210] 12. The cationic cellulose fibers of aspect 11, wherein the untreated cellulose fibers are separated from cotton, flax, hemp, jute and / or ramie.

[0211] 13. Cationic cellulose fibers of aspect 11, wherein the untreated cellulose fibers are separated from cotton.

[0212] 14. Aspect 11 of cationic cellulose fibers, wherein the untreated cellulose fibers are isolated from hemp.

[0213] 15. The cationic cellulose fiber of aspect 11, wherein the cationic reagent is a quaternary ammonium salt.

[0214] 16. The cationic cellulose fiber of aspect 11, wherein the cationic reagent is selected from N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride and 1-propanediol-N,N'-(oxydi-2,1-ethylenediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl]dichloride.

[0215] 17. The cationic cellulose fiber of aspect 11, wherein the cationic reagent is N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride.

[0216] 18. The cationic cellulose fiber of aspect 11, wherein the cationic reagent is 1-propanenyl-N,N'-(oxydi-2,1-ethylenediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl]dichloride.

[0217] 19. The cationic cellulose fiber of aspect 11, wherein the alkali is sodium hydroxide.

[0218] 20. The cationic cellulose fiber of aspect 11, wherein the ratio of cationic reagent to alkali in the cationic treatment solution is in the range of about 10:1 to about 1:10.

[0219] 21. The cationic cellulose fiber of aspect 11, wherein the ratio of cationic reagent to alkali in the cationic treatment solution is in the range of about 10:1 to about 1:1.

[0220] 22. The cationic cellulose fiber of aspect 11, wherein the ratio of cationic reagent to alkali in the cationic treatment solution is approximately 2:1.

[0221] 23. The cationic cellulose fiber of aspect 11, wherein the ratio of cationic treatment solution to untreated cellulose fiber is approximately 10:1 to approximately 1:10.

[0222] 24. Aspect 11 of cationic cellulose fibers, wherein the ratio of cationic treated solution to untreated cellulose fibers is approximately 2:1.

[0223] 25. Aspect 11 of cationic cellulose fibers, wherein the ratio of cationic treated solution to untreated cellulose fibers is approximately 1:1.

[0224] 26. The cationic cellulose fiber of aspect 11, wherein the cationic treatment solution further comprises a wetting agent.

[0225] 27. The cationic cellulose fiber of aspect 26, wherein the wetting agent is a fatty alcohol ethoxylate compound (Albaflow Conti). ® ).

[0226] 28. The cationic cellulose fiber of aspect 11, wherein the cationic treatment solution further comprises an antifoaming agent.

[0227] 29. The cationic cellulose fiber of aspect 11, wherein the impregnated cellulose fiber is heated by conveying it through a heating device selected from a heating bath, a steam chamber, a drying cylinder column, and a hot air chamber.

[0228] 30. The cationic cellulose fiber of aspect 11, wherein the method further comprises drying the impregnated cellulose fiber in an infrared pre-dryer prior to the heating step.

[0229] 31. The cationic cellulose fiber of aspect 11, wherein the processing includes neutralizing, rinsing and drying the fixed cationic cellulose fiber.

[0230] 32. The cationic cellulose fiber of aspect 11, wherein the processing further comprises sizing the cationic fiber and winding it onto a warp beam for weaving.

[0231] 33. A cationic fabric comprising the cationic cellulose fibers of aspect 1.

[0232] 34. The cationic fabric of aspect 33 is essentially colorless.

[0233] 35. The cationic fabric of aspect 33 is gray.

[0234] 36. The cationic fabric of aspect 33 is natural in color.

[0235] 37. The cationic fabric of aspect 33, which is prepared by a method comprising the following steps: Provide cationic cellulose fibers as warp yarns for weaving; and Cationic cellulose fibers are woven together with untreated weft yarns to obtain cationic fabrics.

[0236] 38. A garment comprising the cationic fabric of aspect 33.

[0237] 39. The garments in aspect 38 are basically colorless.

[0238] 40. The garment in section 38 is gray.

[0239] 41. The ready-to-wear garments in aspect 38 are natural in color.

[0240] 42. Garments in aspect 38, which are dyed garments.

[0241] 43. The garment in aspect 42 has a mixed color effect.

[0242] 44. The garment in aspect 42 has a denim-like appearance.

[0243] 45. The garment of aspect 39, which is essentially colorless, is prepared by a method comprising the following steps: Provide cationic fabrics; and The cationic fabric is shaped into essentially colorless garments.

[0244] 46. ​​The method of aspect 45, wherein the forming comprises cutting and / or sewing cationic fabric into a substantially colorless garment.

[0245] 47. The garment of aspect 42, which is a dyed garment, is prepared by a method comprising the following steps: Provide cationic fabrics; Cationic fabrics are shaped into essentially colorless garments; The essentially colorless garments are immersed in a dye bath solution containing water and a wetting agent to form pretreated garments; and The pretreated garment is reacted with anionic dye, wherein the reaction comprises gradually adding the anionic dye to a dye bath solution containing the pretreated garment, wherein the dye bath solution is substantially free of salt and alkaline contents.

[0246] 48. Garments of aspect 47, wherein the forming includes cutting and / or sewing cationic fabrics into substantially colorless garments.

[0247] 49. Garments of aspect 47, wherein the substantially colorless garments are constructed such that the outer portions of the garments face outward prior to the reaction steps.

[0248] 50. Garments in aspect 47, wherein the wetting agent is a fatty alcohol ethoxylate compound (Albaflow Conti). ® ).

[0249] 51. Garments of aspect 47, wherein the concentration of the wetting agent is from about 0.1 g / L to about 10 g / L.

[0250] 52. Garments of aspect 47, wherein the concentration of wetting agent is approximately 0.5 g / L.

[0251] 53. Garments in aspect 47, wherein anionic dyes are direct dyes, reactive dyes, or acid dyes.

[0252] 54. Garments of aspect 47, wherein the anionic dye contains SO3Na groups.

[0253] 55. In the garments of aspect 47, the anionic dyes are acid dyes.

[0254] 56. In aspect 47 of the ready-made garments, anionic dyes are direct dyes.

[0255] 57. Apparel in aspect 47, where the anionic dye is a reduced sulfur dye.

[0256] 58. In aspect 47 of the garments, anionic dyes are reactive dyes.

[0257] 59. In the garments of aspect 58, the reactive dyes are bifunctional reactive dyes.

[0258] 60. Apparel in aspect 58, of which reactive dyes are high molecular weight reactive dyes.

[0259] 61. Apparel in aspect 58, in which the reactive dye is Everzol ED dye.

[0260] 62. Garments in aspect 58, where the reactive dye is vinyl sulfone (Remazol). ® )dye.

[0261] 63. Garments of aspect 47, wherein the anionic dye is a bifunctional dye containing a vinyl sulfone moiety.

[0262] 64. Garments of aspect 47, wherein the weight ratio of substantially colorless garments to the weight of dye bath solution is in the range of approximately 1:4 to approximately 1:50.

[0263] 65. Garments in aspect 47, wherein the dye bath solution is essentially free of sodium chloride and sodium sulfate.

[0264] 66. Garments of aspect 47, wherein the dye bath solution further comprises a dispersant and / or a leveling agent.

[0265] 67. Garments of aspect 66, wherein the dispersant and / or leveling agent is a lignin sulfonate.

[0266] 68. Garment of aspect 47, wherein the reaction steps are carried out at ambient room temperature.

[0267] 69. Garments of aspect 47, wherein the reaction steps are carried out at a temperature in the range of approximately 65°C to approximately 90°C.

[0268] 70. Garment of aspect 47, wherein the reaction step is carried out at a temperature of 85°C.

[0269] 71. Garments of aspect 47, wherein the duration of the reaction step is approximately 5 minutes to approximately 30 minutes.

[0270] 72. Garment of aspect 47, wherein the duration of the reaction step is approximately 15 minutes.

[0271] 73. Garments of aspect 47, wherein the reaction steps include gradually adding anionic dye to a dye bath solution and then reacting for about 10 minutes, then raising the dye bath temperature to a temperature of 85°C at a rate of 1°C / min and then reacting for about 15 minutes.

[0272] 74. The garment of aspect 47 further includes a replenishing step, wherein after the reaction step, the dye bath is drained and subsequently replenished with a second dye bath solution containing water, a wetting agent and anionic dye.

[0273] 75. The garment of aspect 47 further includes a cold rinsing step after the reaction step, in which the dye bath solution is drained and the garment is cold rinsed and dried.

[0274] 76. For garments in section 75, the duration of the cold rinse step is approximately 5 to approximately 20 minutes.

[0275] 77. For garments in section 75, the cold rinse step lasts for approximately 10 minutes.

[0276] 78. Garments of aspect 47, wherein the colorless garment is pre-shrinked prior to the reaction step.

[0277] 79. A method for preparing cationic cellulose fibers of aspect 1, comprising: reacting untreated cellulose fibers with a cationic treatment solution containing a cationic reagent and a base.

[0278] 80. A method of aspect 79, wherein untreated cellulose fibers are separated from cotton, flax, hemp, jute and / or ramie.

[0279] 81. A method of aspect 79, wherein untreated cellulose fibers are separated from cotton.

[0280] 82. A method of aspect 79, wherein untreated cellulose fibers are isolated from cannabis.

[0281] 83. The method of aspect 79, wherein the untreated cellulose fibers are yarn fibers.

[0282] 84. The method of aspect 83, wherein the yarn fiber is one of the warp fiber or the weft fiber.

[0283] 85. The method of aspect 83, wherein the untreated cellulose fibers are either in the form of raw slivers or cooked slivers.

[0284] 86. The method of aspect 83, wherein the untreated cellulose fibers are in the form of raw strips.

[0285] 87. The method of aspect 83, wherein the untreated cellulose fibers are in the form of slivers.

[0286] 88. The method of aspect 79, wherein the cationic reagent is a quaternary ammonium salt.

[0287] 89. The method of aspect 79, wherein the cation reagent is selected from N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride and 1-propanediol-N,N'-(oxydi-2,1-ethylenediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl]dichloride.

[0288] 90. The method of aspect 79, wherein the cationic reagent is N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride.

[0289] 91. The method of aspect 79, wherein the cation reagent is 1-propanenyl-N,N'-(oxydi-2,1-ethylenediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl]dichloride.

[0290] 92. The method of aspect 79, wherein the base is sodium hydroxide.

[0291] 93. The method of aspect 79, wherein the ratio of the cation reagent to the base in the reaction step is in the range of about 10:1 to about 1:10.

[0292] 94. The method of aspect 79, wherein the ratio of the cation reagent to the base in the reaction step is in the range of about 10:1 to about 1:1.

[0293] 95. The method of aspect 79, wherein the ratio of the cationic reagent to the base in the reaction step is approximately 2:1.

[0294] 96. Aspect 79 of the method, wherein the ratio of cationic treatment solution to untreated cellulose fibers is approximately 10:1 to approximately 1:10.

[0295] 97. The method of aspect 79, wherein the ratio of cationic treatment solution to untreated cellulose fibers is approximately 2:1.

[0296] 98. Aspect 79 of the method, wherein the ratio of cationic treatment solution to untreated cellulose fibers is approximately 1:1.

[0297] 99. Aspect 79 of the method, wherein the cation treatment solution further comprises a wetting agent.

[0298] 100. The method of aspect 99, wherein the wetting agent is a fatty alcohol ethoxylate compound (Albaflow Conti) ® ).

[0299] 101. Aspect 79 of the method, wherein the cationic treatment solution further comprises an antifoaming agent.

[0300] 102. Aspect 79 of the method, wherein the duration of the reaction step is less than about 15 minutes.

[0301] 103. Aspect 79 of the method, wherein the duration of the reaction step is less than about 10 minutes.

[0302] 104. The method of aspect 79, wherein the duration of the reaction step is approximately 10-15 minutes.

[0303] 105. The method of aspect 79, wherein the reaction step is carried out under heating.

[0304] 106. A method of aspect 79, wherein the reaction steps are carried out at a temperature of about 50°C to about 100°C.

[0305] 107. The method of aspect 79, wherein the reaction steps are carried out at a temperature of approximately 85°C.

[0306] 108. A method of aspect 79, wherein the reaction step is carried out by heating the reaction to its boiling point.

[0307] 109. A method of aspect 79, wherein the reaction step is carried out in textile machinery.

[0308] 110. A method of aspect 105, wherein the heat source is steam passing through heating coils of textile machinery.

[0309] 111. Aspect 105 of the method, wherein the heat source is a stainless steel roller of a textile machine.

[0310] 112. The method of aspect 105, wherein the heat source is from the steam chamber of the textile machinery.

[0311] 113. A method of aspect 79, wherein the reaction steps are carried out without heating.

[0312] 114. A method of aspect 79, wherein the reaction steps are carried out in textile machinery without heating, and includes the step of impregnating cellulose fibers with a treatment solution containing a cationic reagent and an alkali.

[0313] 115. The method of aspect 114, wherein immersion is carried out in an airless environment for 18-24 hours.

[0314] 116. A method of aspect 79, wherein the method further includes a step of separating crude cationic cellulose fibers after the reaction step.

[0315] 117. A method of aspect 116, wherein crude cationic cellulose fibers are washed and neutralized with acid to obtain purified cationic cellulose fibers.

[0316] 118. The method of aspect 117, wherein the acid is citric acid.

[0317] 119. The method of aspect 117, wherein washing and neutralization eliminate undesirable amine odors.

[0318] 120. A method of aspect 79, wherein untreated cellulose fibers are treated with a cationic treatment solution by a yarn treatment sizing machine.

[0319] 121. The method of aspect 120, wherein the yarn processing sizing machine is equipped with a heating device.

[0320] 122. A method of aspect 79, wherein untreated cellulose fibers are treated with a cationic treatment solution in a tube dyeing machine.

[0321] 123. A method for preparing cationic cellulose fibers according to aspect 1, comprising: Untreated cellulose fibers are immersed in a cationic treatment solution to form saturated cellulose fibers using a yarn treatment sizing machine, wherein the cationic treatment solution contains a cationic reagent and an alkali. Saturated cellulose fibers are rolled using horizontal extrusion rollers to a liquid content of up to approximately 100% of the weight of untreated cellulose fibers to form rolled cellulose fibers. The cellulose fibers are heated and impregnated to form fixed cationic cellulose fibers; The fixed cationic cellulose fibers are processed to obtain cationic cellulose fibers.

[0322] 124. The method of aspect 123, wherein the impregnated cellulose fibers are heated by conveying them through a heating device selected from a heating bath, a steam chamber, a drying cylinder column, and a hot air chamber.

[0323] 125. The method of aspect 123, wherein the method further comprises drying the impregnated cellulose fibers in an infrared pre-dryer prior to the heating step.

[0324] 126. The method of aspect 123, wherein the processing includes neutralizing, rinsing and drying the fixed cationic cellulose fibers.

[0325] 127. The method of aspect 123, further comprising sizing cationic fibers and winding them onto a warp beam for weaving.

[0326] 128. A method for preparing a cationic fabric from cationic cellulose fibers of aspect 1, comprising: Provide cationic cellulose fibers as warp yarns for weaving; and Cationic cellulose fibers are woven together with untreated weft yarns to obtain cationic fabrics.

[0327] 129. The method of aspect 128, wherein the cationic fabric is substantially colorless.

[0328] 130. The method of aspect 128, wherein the cationic fabric is gray.

[0329] 131. The method of aspect 128, wherein the cationic fabric is natural-colored.

[0330] 132. The method of aspect 128 further includes the step of pre-shrinking the cationic fabric.

[0331] 133. The method of aspect 132, wherein the cationic fabric is pre-shrinked to a residual shrinkage rate of -3%.

[0332] 134. A method for forming regenerated cationic cellulose fibers from a recycling aspect 33 of a cationic fabric, comprising: Cutting cationic fabrics to form multiple cellulose fiber fragments; and Multiple cellulose fiber fragments are reacted with a cationic treatment solution containing a cationic reagent and a base.

[0333] 135. A method for preparing a substantially colorless garment from the cationic fabric of aspect 32, comprising: Provide cationic fabrics; and The cationic fabric is shaped into essentially colorless garments.

[0334] 136. The method of aspect 135, wherein the forming includes cutting and / or sewing cationic fabrics into substantially colorless garments.

[0335] 137. The method of aspect 135, in which essentially colorless garments are gray.

[0336] 138. The method of aspect 135, in which essentially colorless garments are natural-colored.

[0337] 139. A method for preparing dyed garments from the cationic fabric of aspect 33, comprising: Provide cationic fabrics; Cationic fabrics are shaped into essentially colorless garments; The essentially colorless garments are immersed in a dye bath solution containing water and a wetting agent to form pretreated garments; and The pretreated garment is reacted with anionic dye, wherein the reaction comprises gradually adding the anionic dye to a dye bath solution containing the pretreated garment, wherein the dye bath solution is substantially free of salt and alkaline contents.

[0338] 140. The method of aspect 139, wherein the forming includes cutting and / or sewing cationic fabrics into substantially colorless garments.

[0339] 141. A method of aspect 139, wherein a substantially colorless garment is constructed such that the outer portion of the garment faces outward prior to the reaction step.

[0340] 142. The method of aspect 139, wherein the wetting agent is a fatty alcohol ethoxylate compound (Albaflow Conti ® ).

[0341] 143. The method of aspect 139, wherein the concentration of the wetting agent is from about 0.1 g / L to about 10 g / L.

[0342] 144. The method of aspect 139, wherein the concentration of the wetting agent is approximately 0.5 g / L.

[0343] 145. The method of aspect 139, wherein the anionic dye is a direct dye, a reactive dye, or an acid dye.

[0344] 146. A method of aspect 139, wherein the anionic dye contains an SO3Na group.

[0345] 147. The method of aspect 139, wherein the anionic dye is an acid dye.

[0346] 148. The method of aspect 139, wherein the anionic dye is a direct dye.

[0347] 149. The method of aspect 139, wherein the anionic dye is a reduced sulfur dye.

[0348] 150. The method of aspect 139, wherein the anionic dye is a reactive dye.

[0349] 151. A method of aspect 150, wherein the reactive dye is a bifunctional reactive dye.

[0350] 152. The method of aspect 150, wherein the reactive dye is a high molecular weight reactive dye.

[0351] 153. The method of aspect 150, wherein the reactive dye is a bifunctional dye.

[0352] 154. A method of aspect 150, wherein the reactive dye is a vinyl sulfone dye.

[0353] 155. The method of aspect 139, wherein the anionic dye is a bifunctional dye containing at least one vinyl sulfone group.

[0354] 156. The method of aspect 139, wherein the weight ratio of the substantially colorless garment to the dye bath solution is in the range of approximately 1:4 to approximately 1:50.

[0355] 157. The method of aspect 139, wherein the dye bath solution is substantially free of sodium chloride and sodium sulfate.

[0356] 158. The method of aspect 139, wherein the dye bath solution further comprises a dispersant and / or a leveling agent.

[0357] 159. The method of aspect 158, wherein the dispersant and / or leveling agent is a lignin sulfonate.

[0358] 160. The method of aspect 139, wherein the reaction steps are carried out at ambient room temperature.

[0359] 161. The method of aspect 139, wherein the reaction steps are carried out at a temperature in the range of about 65°C to about 90°C.

[0360] 162. The method of aspect 139, wherein the reaction step is carried out at a temperature of 85°C.

[0361] 163. The method of aspect 139, wherein the duration of the reaction step is from about 5 minutes to about 30 minutes.

[0362] 164. The method of aspect 139, wherein the duration of the reaction step is approximately 15 minutes.

[0363] 165. A method of aspect 139, wherein the reaction steps include gradually adding an anionic dye to a dye bath solution and then reacting for about 10 minutes, then increasing the dye bath temperature to a temperature of 85°C at a rate of 1°C / min and then reacting for about 15 minutes.

[0364] 166. The method of aspect 139 further includes a replenishing step, wherein after the reaction step, the dye bath is drained and subsequently replenished with a second dye bath solution containing water, a wetting agent and an anionic dye.

[0365] 167. The method of aspect 139 further includes a cold rinsing step after the reaction step, in which the dye bath solution is drained and the garment is cold-rinsed and drained.

[0366] 168. The method of aspect 167, wherein the duration of the cold rinsing step is approximately 5 minutes to approximately 20 minutes.

[0367] 169. The method of aspect 167, wherein the duration of the cold rinsing step is approximately 10 minutes.

[0368] 170. The method of aspect 139, wherein the colorless garment is pre-shrinked prior to the reaction step.

[0369] 171. Aspect 139 method, wherein the dyed garment has a color mixing effect.

[0370] 172. Aspect 139 of the method, wherein the dyed garment has a denim-like appearance.

[0371] 173. A method for manufacturing garments from ring-dyed core yarn, comprising: The preparation of cationic cellulose fibers includes the following steps: The outer layer, containing multiple covalently linked cation portions, is treated; and The processing steps leave an inner layer that is essentially free of cationic charge; Cationic cellulose fibers are woven into undyed cationic fabrics; Undyed cationic fabrics are shaped into essentially colorless garments and cutting and sewing waste; Dyeing essentially colorless garments with anionic dyes; and Cutting and sewing waste is reprocessed into undyed cationic yarn.

[0372] 174. A method of aspect 173, wherein undyed cationic yarns are woven into undyed cationic fabrics.

[0373] 175. The method of aspect 173, wherein the reprocessing steps include cutting and grinding the cutting and sewing waste.

[0374] 176. A cationic cellulose yarn comprising: The outer layer contains multiple covalently linked cation moieties; and The inner layer is essentially free of cationic charges. The thickness of the multiple covalently linked cations gradually decreases from the outer layer to the inner layer.

[0375] 177. An anion-dyed cellulose yarn comprising: The surface layer of yarn that absorbs the maximum proportion of anionic dyes; The inner core of yarns that do not absorb anionic dyes; and The yarn has a gradient layer between the surface layer and the inner core, wherein the gradient layer absorbs varying amounts of anionic dye depending on its distance from the surface layer.

[0376] 178. Anionic dyed cellulose yarn of aspect 177, wherein the amount of anionic dye absorbed by the gradient layer is at its maximum near the surface layer and at its minimum near the core.

[0377] 179. A keratin fiber that can form a ring-dyed core yarn when treated with anionic dyes.

[0378] 180. An anion-stained keratin yarn comprising: The surface layer of yarn that absorbs the maximum proportion of anionic dyes; The inner core of yarns that do not absorb anionic dyes; and The yarn has a gradient layer between the surface layer and the inner core, wherein the gradient layer absorbs varying amounts of anionic dye depending on its distance from the surface layer.

[0379] 181. Anionic dyed keratin yarn of aspect 180, wherein the amount of anionic dye absorbed by the gradient layer is at its maximum near the surface layer and at its minimum near the core.

[0380] 182. Keratin fibers of aspect 179, wherein keratin is derived from the hair, nails, feathers, horns or claws of mammals.

[0381] 183. Keratin fibers of aspect 179, wherein keratin is derived from wool.

[0382] 184. A keratin fabric comprising keratin fibers of aspect 179.

[0383] 185. Keratin fabric of aspect 184, which is essentially colorless.

[0384] 186. Keratin fabric of aspect 184, which is gray.

[0385] 187. Keratin fabric of aspect 184, which is natural in color.

[0386] 188. A keratin fabric of aspect 184, which is prepared by a method comprising the following steps: Provide keratin fibers as warp yarns for weaving; and Keratin fibers are woven together with untreated weft yarns to obtain keratin fabrics.

[0387] 189. A garment comprising a keratin fabric comprising aspect 184.

[0388] 190. The ready-to-wear garments of aspect 189 are basically colorless.

[0389] 191. The garment in section 189 is gray.

[0390] 192. The ready-to-wear garments of aspect 189 are natural in color.

[0391] 193. Apparel of aspect 189, which is dyed garment.

[0392] 194. The ready-to-wear garments in aspect 193 have a mixed color effect.

[0393] 195. Aspect 42 of ready-to-wear garments, which have a denim-like appearance.

[0394] 196. A garment of aspect 190, which is essentially colorless, is prepared by a method comprising the following steps: Provide keratin fabrics; and Keratin fabric is shaped into essentially colorless garments.

[0395] 197. The method of aspect 196, wherein the forming includes cutting and / or sewing keratin fabric into a substantially colorless garment.

[0396] 198. Garments of aspect 193, which are dyed garments, are prepared by a method comprising the following steps: Provide keratin fabrics; Shape keratin fabrics into essentially colorless garments; The essentially colorless garments are immersed in a dye bath solution containing water and a wetting agent to form pretreated garments; and The pretreated garment is reacted with anionic dye, wherein the reaction comprises gradually adding the anionic dye to a dye bath solution containing the pretreated garment, wherein the dye bath solution is substantially free of salt and alkaline contents.

[0397] 199. A fabric comprising: At least one of treated cellulose fibers and treated keratin fibers, which are treated to accept anionic dyes and form ring-dyed core yarns; At least one of untreated cellulose fibers and untreated keratin fibers; Among them, ring-dyed core yarn is one of the warp or weft yarns of the fabric; and At least one of the untreated cellulose fibers and untreated keratin fibers is another type of warp or weft yarn from ring-dyed core yarn.

[0398] 200. Method of aspect 105, wherein the heat source is from the hot air chamber.

[0399] 201. A regenerated cationic cellulose fiber prepared by the method of aspect 134, wherein the regenerated cationic cellulose fiber is capable of forming a ring-dyed core yarn when treated with anionic dyes, wherein the ring-dyed core has a speckled appearance.

Claims

1. A cationic cellulose fiber comprising: The outer layer contains multiple covalently linked cation moieties; and The inner layer is essentially free of cationic charges. The outer layer to the inner layer has a thickness ratio in the range of about 10:1 to about 1:10, and the cationic portion is derived from a quaternary ammonium salt.

2. The cationic cellulose fiber according to claim 1 is a yarn fiber.

3. The cationic cellulose fiber according to claim 1, wherein it is a warp fiber.

4. The cationic cellulose fiber of claim 1, wherein the cationic portion is derived from N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride and / or 1-propanediyl-N,N'-(oxydi-2,1-ethylenediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl]dichloride.

5. The cationic cellulose fiber of claim 1, prepared by a method comprising the following steps: Untreated cellulose fibers are immersed in a cationic treatment solution using a yarn treatment sizing machine to form saturated cellulose fibers, wherein the cationic treatment solution contains a cationic reagent and an alkali. The saturated cellulose fibers are rolled using horizontal extrusion rollers to a liquid content of up to approximately 100% of the weight of the untreated cellulose fibers to form rolled cellulose fibers. The impregnated cellulose fibers are heated to form fixed cationic cellulose fibers; and The fixed cationic cellulose fibers are processed to form the cationic cellulose fibers.

6. The cationic cellulose fiber of claim 5, wherein the ratio of the cationic reagent to the alkali in the cationic treatment solution is in the range of about 10:1 to about 1:

10.

7. The cationic cellulose fiber of claim 5, wherein the ratio of the cationic treatment solution to the untreated cellulose fiber is approximately 1:

1.

8. The cationic cellulose fiber of claim 5, wherein the heating is performed by conveying the impregnated cellulose fiber through a heating device selected from a heating bath, a steam chamber, a drying cylinder column, and a hot air chamber.

9. A cationic fabric comprising the cationic cellulose fibers of claim 1.

10. The cationic fabric of claim 9, which is substantially colorless.

11. The cationic fabric of claim 9, prepared by a method comprising the following steps: The cationic cellulose fibers are provided as warp yarns for weaving; and The cationic cellulose fibers are woven together with untreated weft yarns to obtain a cationic fabric.

12. A garment comprising the cationic fabric of claim 9.

13. The garment of claim 12, which is substantially colorless.

14. The garment of claim 12, wherein it is a dyed garment.

15. The garment of claim 12, having a denim-like appearance.

16. The garment of claim 12, which is a dyed garment, prepared by a method comprising the following steps: Provide the cationic fabric; The cationic fabric is shaped into a substantially colorless garment; The substantially colorless garment is immersed in a dye bath solution containing water and a wetting agent to form a pretreated garment; as well as The pretreated garment is reacted with anionic dye, wherein the reaction comprises gradually adding the anionic dye to the dye bath solution containing the pretreated garment, wherein the dye bath solution is substantially free of salt and alkaline contents.

17. The garment of claim 16, wherein the anionic dye is a direct dye, a reactive dye, or an acid dye.

18. The garment of claim 16, wherein the weight ratio of the substantially colorless garment to the weight of the dye bath solution is in the range of about 1:4 to about 1:

50.

19. The garment of claim 16, wherein the dye bath solution is substantially free of sodium chloride and sodium sulfate.

20. A method of recycling the cationic fabric of claim 9 to form regenerated cationic cellulose fibers, comprising: The cationic fabric is cut to form multiple cellulose fiber fragments; as well as The plurality of cellulose fiber fragments are reacted with a cationic treatment solution containing a cationic reagent and a base.

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