Patent Application
20250122667
The present invention relates to cationic cellulosic fibers that are useful for preparing dyeable fabrics and garments, for example, garments that have a mélange effect and/or a denim-like in appearance.
Since the introduction of the indigo dyed denim technology over a hundred years ago, indigo dyed denim garments have become one of the dominating fashions in the garment business. Although indigo is classified as a vat dye, it really does not possess the all-round fastness properties that other vat dyes are known to possess. Moreover, the substantivity of the indigo on cotton yarn is comparatively low. For these reasons, indigo denim warp yarns can only be dyed by using a multi dipping process on either a rope dyeing system or a slasher dyeing system to obtain an indigo blue shade with a characteristic “ring-dyed effect.” Ring dyeing occurs when dyes are only partially diffused to the interior of a fiber, with most of the dye stained onto the fiber surface, forming a layer of dye on the surface and little to no dye in the core; thereby forming around the fiber a ring-like appearance of the dye that can be viewed cross-sectionally. This unique appearance of the denim fabrics has become a signature look that is well received by the denim fashion industry. Subsequently, the production of the denim garments skyrocketed globally resulting in significant market shares in the garment business.
Although the worn down look evolved from the ring-dyed indigo denim fabrics is appealing to denim garment designers, a problem still exists with the indigo dyed denim. Due to its poor rubbing fastness, an undesirable blue tint can sometimes be stained on light colored clothing and fabric surfaces. Moreover, the conventional denim dyeing process uses large quantities of dye, water, salts, and other substances which are toxic and harmful to the environment.
In recent years, the application of cationic agents on cellulose fibers has been an area of active research. It has been found that when cellulose materials are treated with cationic chemicals, the dyeing properties of the treated cellulose are markedly improved. Much deeper dyeing, and lesser chemical usage and dye consumption are possible even without using salt and alkali in the reactive dyeing. Unfortunately, however, use of cationic agents often cause problems with the evenness of the treatment on the fabrics, and create issues with controlling the dye strike to produce level dyed fabrics. These imperfections have hindered commercializing this chemistry in many textile applications.
The cationic agent most commonly used is Quat 188®, manufactured by Dow Chemical Company. This cationic agent, in the presence of optimum amount of alkali, is converted to an active epoxide form that reacts with the hydroxyl groups of cellulose material (e.g., cellulose-based yarn fibers), thereby forming a covalent bond allowing the cationic dye site of the agent to be anchored permanently onto the cellulose material. This cationic site changes the dying behavior of the cellulose material allowing it to pick up reactive and other anionic dyes without the assistance of other extra chemical auxiliaries. However, while the epoxy group can react with the hydroxyl groups in cellulose, it can also undergo hydrolysis in water and becomes deactivated. Because of this instability, alkali and sodium hydroxide must be added into the treatment bath and the bath solution must be used within 15 minutes, or a tailing effect will occur. Subsequent washing the cellulose material with citric acid is also required to eliminate an undesirable amine odor.
Another cationic agent that is known in the textile field is EcoFast Pure®, from the Dow Chemical Company. EcoFast Pure advantageously possesses two epoxy groups, whereas Quat 188 only possesses one epoxy group. Since EcoFast contains more than one epoxy group, even if one epoxy group is hydrolyzed during the epoxidation reaction, the agent still remains functional and is available to react with the cellulose material with the remaining epoxy group. Therefore, EcoFast Pure has a higher fixation yield and a more stable bath than QUAT 188. Another advantage of EcoFast Pure is that it does not generate amine odor. Since the cationic agent itself does not have affinity to the cellulose material, the level of its fixation on the cellulose depends on the concentration of the agent. This is because only the activated cationic agent in direct contact with the cellulose material is able to have reaction with the cellulose material, while the cationic agent not in direct contact with the cellulose is hydrolyzed and becomes deactivated. Unfortunately, this feature that requires using high liquor ratio machines is not workable because of the high chemical cost, making cationic chemistry unsuitable for bulk commercialization.
Accordingly, there is a need in the art for a commercially viable and environmentally friendly method of dyeing garments that can be responsive to the rapid changes in product demand in the textile industry. The materials and methods described herein are directed to these and other ends.
The present invention described herein provides a cationic cellulosic fiber. The cationic cellulosic fiber comprises an outer layer comprising a plurality of covalently attached cationic moieties; and an inner layer that is substantially free of cationic charge, wherein a thickness ratio of the outer layer to the inner layer is in the range of about 10:1 to about 1:10.
The present invention further provides a cationic fabric comprising the cationic cellulosic fiber. The cationic fabric may be a substantially colorless fabric (e.g., grey and/or greige).
The present invention further provides a garment comprising the cationic fabric. The garment may be a substantially colorless garment and/or a dyed garment (e.g., having a mélange effect and/or a denim-like appearance).
The present invention further provides a method of preparing the cationic cellulosic fiber having steps of immersing an untreated cellulosic fiber into a cationic treatment solution through a yarn treatment slasher machine to form a saturated cellulosic fiber, wherein the cationic treatment solution comprises a cationic agent and an alkali; padding the saturated cellulosic fiber though a horizontal squeeze roll to a liquor pick-up of up to about 100% of the weight of the untreated cellulosic fiber to form a padded cellulosic fiber; heating the padded cellulosic fiber to form a fixated cationic cellulosic fiber; and processing the fixated cationic cellulosic fiber to form the cationic cellulosic fiber.
The present invention further provides a method of preparing the cationic fabric from the cationic cellulosic fiber by providing the cationic cellulosic fiber as a warp yarn for weaving; and weaving the cationic cellulosic fiber with an untreated weft yarn to yield a cationic fabric.
The present invention further provides a method of recycling the cationic fabric to form a regenerated cationic cellulosic fiber, with steps of cutting the cationic fabric to form a plurality of cellulosic fiber fragments; and reacting the plurality of cellulosic fiber fragments with a cationic treatment solution comprising a cationic agent and an alkali.
The present invention further provides a method of preparing a substantially colorless garment from the cationic fabric by providing the cationic fabric; and shaping the cationic fabric into a substantially colorless garment.
The present invention further provides a method of making a dyed garment from the cationic fabric by providing the cationic fabric; shaping the cationic fabric into a substantially colorless garment; immersing the substantially colorless garment in a dye bath solution comprising water and a wetting agent to form a pre-treated garment; and reacting the pre-treated garment with an anionic dye, wherein the reacting involves gradually adding the anionic dye to the dye bath solution containing the pre-treated garment, wherein the dye bath solution is substantially free of salt and alkaline content.
The present invention further provides a method of preparing a garment from a ring dyed core yarn, by preparing a cationic cellulosic fiber comprising the steps of: treating an outer layer comprising a plurality of covalently attached cationic moieties; and leaving an inner layer that is substantially free of cationic charge after the treating step; weaving the cationic cellulosic fiber into an undyed cationic fabric; shaping the undyed cationic fabric into: a substantially colorless garment; and cut-and-sew waste; dyeing the substantially colorless garment with an anionic dye; and reprocessing the cut-and-sew waste into an undyed cationic yarn.
The present invention further provides a cationic cellulosic yarn having an outer layer comprising a plurality of covalently attached cationic moieties; and an inner layer that is substantially free of cationic charge, wherein the plurality of covalently attached cationic moieties gradually decreases through a thickness of the outer layer toward the inner layer.
The present invention further provides an anionic dyed cellulosic yarn including a surface layer of the yarn absorbing the largest proportion of the anionic dye; an inner core of the yarn absorbing none of the anionic dye; and a gradation layer of the yarn between the surface layer and the inner core, wherein the gradation layer absorbs a varying amount of the anionic dye depending on the distance from the surface layer.
The present invention involves using cationic chemistry to produce a colorless fabric, whereby dyeing in garment form with anionic dyes (e.g., reactive or direct dyes) results in a “mélange effect,” e.g., affording the unique denim look similar to that of the indigo dyed denim. Since reactive dyes can be used in the inventive process, the problem of rubbing fastness in the conventional indigo denim dyeing process is overcome. Moreover, the garments of the invention can be dyed into a wide range of color shades, as opposed to the indigo denim that can only produce different depths of blue shades (see
Instead of treating in fabric form, the inventive process permits cationic treatment of the yarn (e.g., warp yarn) to be woven with untreated yarn into a denim-like fabric but with no color at the fabric stage. The formulated cationic chemical solution pick-up is approximately 60-80% of the warp weight being treated. The process of the invention is considered eco-friendly because the reactive dyes in the bath are completely exhausted, and the insignificant amount of leftover chemicals used during dyeing can be easily recycled.
The warp yarns used are the same as for use in the indigo dyeing process. As shown in
In some embodiments, the present invention provides, inter alia, a cationic cellulosic fiber comprising an outer layer comprising a plurality of covalently attached cationic moieties; and an inner layer that is substantially free of cationic charge, wherein a thickness ratio of the outer layer to the inner layer is in the range of about 10:1 to about 1:10.
In some embodiments, the cationic cellulosic fiber is a yarn fiber. The term “yarn fiber,” as used herein, is to be understood to include all usual fiber types, such as filaments of practically unlimited length as well as shorter fibers. In certain embodiments, the yarn fiber of this invention comprises filaments having a suitable length for use in textile product fabrication.
In some embodiments, the cationic cellulosic fiber is a warp yarn fiber. In other embodiments, the cationic cellulosic fiber is a weft yarn fiber. Warp and weft are the two basic components in weaving to transform yarn into woven fabrics. The vertical warp yarns are held stationary in tension on a loom while the horizontal weft yarn is inserted over and under the warp yarn.
In some embodiments, the cellulosic fiber of the invention is in carded and/or drawn sliver form.
In some embodiments, the cationic cellulosic fiber is in carded form.
In some embodiments, the cationic cellulosic fiber is in sliver form, e.g., drawn sliver form.
Conversion of raw cotton bales into drawn slivers involves passing open and blown-cleaned cotton fibers through a carding machine that removes the short fibers from the raw cotton to form carded slivers. They are then passed through a draw frame to become stronger and better fiber-aligned drawn slivers so that subsequent processing is clean with reduced cotton lint.
In some embodiments, the cationic cellulosic fiber of the invention contains cationic moieties on the outer layer and/or surface of the fiber.
In some embodiments, the cationic moieties are functional groups that are derived from a quaternary ammonium salt. The cationic moieties can be derived from, for example, compounds such as N-(3-chloro-2-hydroxypropyl)trimethyl ammonium chloride (Quat 188; manufactured by Dow Chemicals Inc.) and/or 1-propanaminium, N,N′-(oxydi-2,1-ethanediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl-, dichloride (EcoFast Pure, CAS #96320-92-2; manufactured by Dow Chemicals Inc.), the structures of which are shown below.
In some embodiments, the cationic cellulosic fiber of the invention is derived from N-(3-chloro-2-hydroxypropyl)trimethyl ammonium chloride.
In some embodiments, the cationic moieties are derived from 1-propanaminium,N,N′-(oxydi-2,1-ethanediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl dichloride.
In some embodiments, the ratio of the outer layer to the inner layer of the cationic cellulosic fiber is in the range of about 10:1 to about 1:10. In some embodiments, the ratio of the outer layer to the inner layer is about 1:1.
In some embodiments, the inner layer of the cationic cellulosic fiber is substantially free of cationic charge. In some embodiments, there is no cationic charge in the inner layer.
In some embodiments, the plurality of covalently attached cationic moieties gradually decreases through a thickness of the outer layer toward the inner layer.
In some embodiments, the cationic cellulosic fiber is prepared by a process having the steps of:
The untreated cellulosic fiber can be a synthetic fiber and/or isolated from natural sources and/or a blend of synthetic and natural fibers. In some embodiments, the untreated cellulosic fiber is isolated from cotton, flax, hemp, jute, and/or ramie.
In some embodiments, the untreated cellulosic fiber is isolated from cotton. In some embodiments, the untreated cellulosic fiber is isolated from hemp.
In some embodiments, the cationic treatment solution is any solution that contains a cationic agent that can at least partially react with cellulosic fiber and install a positive charge by, e.g., covalent attachment of a positively charged chemical moiety to the surface of the cellulosic fiber.
In some embodiments, the cationic agent is a quaternary ammonium salt, such as, e.g., N-(3-chloro-2-hydroxypropyl)trimethyl ammonium chloride and/or 1-propanaminium, N,N′-(oxydi-2,1-ethanediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl dichloride.
In some embodiments, the cationic agent is N-(3-chloro-2-hydroxypropyl)trimethyl ammonium chloride (Quat 188).
In some embodiments, the cationic agent is 1-propanaminium,N,N′-(oxydi-2,1-ethanediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl dichloride (EcoFast Pure).
In some embodiments, the cationic treatment solution further comprises an alkali. Without being bound by any particular theory of invention, it is believed that when the cationic agent is reacted in the presence of an optimum amount of alkali, that the cationic agent is converted to an active epoxide form that reacts with the hydroxyl groups of the cellulose material, thereby forming a covalent bond that allows cationic functionality to be to be anchored permanently onto the cellulose material.
In some embodiments, the alkali is a basic, ionic salt, oxide or hydroxide of an alkali metal.
In some embodiments, the alkali is sodium hydroxide.
In some embodiments, the ratio of the cationic agent to alkali in the cationic treatment solution is in the range of about 10:1 to about 1:10.
In some embodiments, the ratio of cationic agent to alkali in the cationic treatment solution is in the range of about 10:1 to about 1:1.
In some embodiments, the ratio of cationic agent to alkali in the cationic treatment solution is about 2:1.
In some embodiments, the ratio of cationic treatment solution to untreated cellulosic fiber is about 10:1 to about 1:10.
In some embodiments, the ratio of cationic treatment solution to untreated cellulosic fiber is about 2:1.
In some embodiments, the ratio of cationic treatment solution to untreated cellulosic fiber is about 1:1.
In some embodiments, the cationic treatment solution can further comprise a wetting agent. A wetting agent can include, e.g., any agent that reduces the surface area of water. The wetting agent can comprise, e.g., a fatty alcohol ethoxylate, such as Albaflow Conti®.
In some embodiments, the cationic treatment solution can further comprise a defoamer. A defoamer can include, e.g., any agent that has “anti-foaming” properties and/or that causes full or partial prevention of foam formation.
In some embodiments, the cationic treatment is followed by a step of padding the saturated cellulosic fiber though a horizontal squeeze roll to a liquor pick-up of about 40% to about 90% (or about 60% to about 80%) of the weight of the untreated cellulosic fiber to form a padded cellulosic fiber.
In some embodiments, the cationic treatment is followed by a step of padding the saturated cellulosic fiber though a horizontal squeeze roll to a liquor pick-up 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 cellulosic fiber to form a padded cellulosic fiber.
In some embodiments, the padded cellulosic fiber is then heated to form a fixated cellulosic fiber.
In some embodiments, the heating is performed by conveying the padded cellulosic fiber through a heating means selected from the group consisting of a heating bath, a steam chamber, a dry can column, and a hot air chamber.
In some embodiments, the method further comprises drying the padded cellulosic fiber in an infrared predryer before the heating step.
In some embodiments, the heating step to form a fixated cationic cellulosic fiber is followed by further processing. The processing can involve, e.g., neutralizing, rinsing and/or drying the fixated cationic cellulosic fiber. The processing can further comprise sizing and winding the cationic fiber onto a loom beam for weaving.
In some embodiments, the invention further provides a cationic fabric comprising the cationic cellulosic fiber. The cationic fabric can be substantially colorless. As used herein, the term “substantially colorless” means that the fabric does not contain virtually any color and/or only mild or neutral coloring (e.g., grey and/or greige).
In some embodiments, the cationic fabric is substantially colorless.
In some embodiments, the cationic fabric is grey.
In some embodiments, the cationic fabric is greige.
In some embodiments, the cationic fabric can be prepared by a process comprising the steps of:
In some embodiments, the invention further provides a garment comprising the cationic fabric. The garment may be substantially colorless (e.g., grey or greige) or it may be a dyed garment.
In some embodiments, the garment is substantially colorless.
In some embodiments, the garment is grey.
In some embodiments, the garment is greige.
In some embodiments, the garment is a dyed garment.
In some embodiments, the garment has a mélange effect. The term “mélange,” as used herein, means a unique two-tone color effect and textured pattern commonly found in conventionally made denim jeans.
In some embodiments, the garment has a denim-like appearance, e.g., it is substantially indistinguishable and/or cannot be distinguished from actual denim based on the look of the garment.
In some embodiments, the invention provides a substantially colorless garment that may be prepared by a process of:
The shaping can comprise, e.g., cutting and/or sewing the cationic fabric into the substantially colorless garment.
In some embodiments, the invention provides a dyed garment that is prepared by a process with the steps of:
Applicant surprisingly discovered that this special combination of method steps results in minimal chemicals and practically no unabsorbed dye remaining in the bath. Both the dye bath and rinse bath can be recycled for use in subsequent dyeing lots; and also effluent discharge is minimal and no landfill is necessary.
In some embodiments, the shaping comprises cutting and/or sewing the cationic fabric into the substantially colorless garment.
In some embodiments, the substantially colorless garment is configured such that the outside portion of the garment is facing outward prior to the reacting step.
In some embodiments, the colorless garment is immersed in a dye bath solution comprising water and a wetting agent to form a pre-treated garment. The wetting agent can be any agent that, e.g., increases the spreading and penetrating properties of a liquid by lowering its surface tension. In some embodiments, the wetting agent is a fatty alcohol ethoxylate compounds, such as Albaflow Conti®.
In some embodiments, the wetting agent is at a concentration of about 0.1 to about 10 g/L.
In some embodiments, the wetting agent is at a concentration of about 0.5 g/L.
In some embodiments, the pre-treated garment is reacted with an anionic dye, wherein the reacting involves gradually adding the anionic dye to the dye bath solution containing the pre-treated garment, wherein the dye bath solution is substantially free of salt and alkaline content.
In some embodiments, the anionic dye is a direct dye, a reactive dye or an acid dye.
In some embodiments, the anionic dye is a direct dye. Direct dyes are water soluble anionic dyes of high molecular weight used for dyeing cellulose materials. They are selected based on the criteria that their light fastness is not affected by the presence of the cationic agents. Those with more SO3Na groups may be useful for certain advantageous properties, e.g., good exhaustion, wash fastness, and heavy earth tone dyeing. In certain embodiments, there is no need to fix the dyes after dyeing as the cationic sites will also act as dye fixing agent to bind up the solubilizing groups. Because of their high affinity to cotton fibers, direct dyes will also dye the untreated cotton weft yarns to give the garments a differential dyeing effect where the treated warp yarns appear darker than the weft yarns. However, the crocking fastness and washing fastness properties of this class of dyes are slightly inferior in some instances to that of the reactive dyes.
In some embodiments, the anionic dye comprises an SO3Na group.
In some embodiments, the anionic dye is an acid dye. Acid dyes are mainly used for dyeing animal fibers and nylon. Due to the anionic nature of this class of dyes in water, they can be used, e.g., to dye garments of the invention to a bright shade, but will not dye or stain the cotton weft yarns of the garment that are not treated with the cationic agent. The dyes can be easily stripped off from the garments in the presence of a mild alkali solution containing as low as 0.5 g/l of soda ash in the stripping bath.
In some embodiments, the anionic dye is a reduced sulfur dye. The reduced sulfur dyes are water insoluble dyes that have to be reduced using alkali and a reducing agent to convert into its soluble anionic form prior to dyeing. The reduced sulfur dyes, just like the direct dyes, can dye both cationic-treated and untreated yarn materials. The garments of the invention can be dyed using the same dyeing procedure as the traditional sulfur dye application.
In some embodiments, the anionic dye is a reactive dye. The reactive dye class possesses a wide color gamut ranging from bright shades to dark navy and deep black. Overall, garments of the invention dyed with reactive dyes possess outstanding washing and rubbing fastness. Bifunctional reactive dyes for exhaustion dyeing application are useful for dyeing garments of the invention. Bifunctional means the dye either possesses 2 identical functional groups or 2 different functional groups. This class of high molecular weight reactive dyes has high substantivity to cotton fiber. The series of reactive dyes known as the Everzol ED (exhaustion dyeing) series by Everlight Inc. have bright shades and high tinctorial power. A dyeing strength of 1 to 1.5% OWM can produce a deep shade, and the dye bath is completely exhausted even without the use of salt and alkali as in the traditional reactive dyeing. This is because the reactive dyes are absorbed by only 25% of the whole inventive cationic-treated garment. The rest of the untreated portion of the garment remains undyed because of the absence of salt and alkali as dyeing auxiliaries.
In some embodiments, the reactive dye is a bifunctional reactive dye.
In some embodiments, the reactive dye is a high molecular weight reactive dye.
In some embodiments, the reactive dye is an Everzol ED dye.
In some embodiments, the reactive dye is a vinyl sulfone (Remazol®) dye.
In some embodiments, the anionic dye is a bifunctional reactive dye that contains at least one vinyl sulfone moiety.
In some embodiments, the ratio of weight of the substantially colorless garment to weight of the dye bath solution is in the range of about 1:4 to about 1:50.
In some embodiments, the dye bath solution is substantially free of sodium chloride and sodium sulphate.
In some embodiments, the dye bath solution further comprises a dispersing agent and/or a leveling agent. The dispersing agent and/or leveling agent can include, e.g., a lignin sulfonate.
In some embodiments, the reacting step is carried out at ambient room temperature. In other embodiments, the reacting step is carried out at temperature in the range of about 65° C. to about 90° C., or at a temperature of 85° C.
In some embodiments, the duration of the reacting step is about 5 to about 30 minutes, or about 15 minutes.
In some embodiments, the reacting step involves gradually adding the anionic dye to the dye bath solution and then reacting for about 10 minutes, after which the dye bath temperature is raised at 1° C./minute to a temperature of 85° C. and then reacted for about 15 minutes.
In some embodiments, reacting step is followed by a replenishing step in which the dye bath is drained after the reacting step and then replenished with a second dye bath solution comprising water, a wetting agent and anionic dye.
In some embodiments, the process to prepare a dyed garment further comprises a cold rinsing step of draining the dye bath solution and cold rinsing the drained garment after the reacting step. The duration of the cold rinsing step can be, e.g., about 5 to about 20 minutes, or about 10 minutes.
In some embodiments, the colorless garment is sanforized prior to the reacting step.
In some embodiments, the invention further provides a method of preparing the cationic cellulosic fiber of the invention, by reacting an untreated cellulosic fiber with a cationic treatment solution comprising a cationic agent and an alkali.
In some embodiments, the untreated cellulosic fiber is isolated from cotton, flax, hemp, jute, and/or ramie.
In some embodiments, the untreated cellulosic fiber is isolated from cotton.
In some embodiments, the untreated cellulosic fiber is isolated from hemp.
In some embodiments, the untreated cellulosic fiber is a yarn fiber.
In some embodiments, the yarn fiber is one of a warp or a weft yarn fiber.
In some embodiments, the untreated cellulosic fiber is in one of carded or drawn sliver form.
In some embodiments, the untreated cellulosic fiber is in carded form.
In some embodiments, the untreated cellulosic fiber is in drawn sliver form.
In some embodiments, the cationic agent is a quaternary ammonium salt.
In some embodiments, the cationic agent is selected from N-(3-chloro-2-hydroxypropyl)trimethyl ammonium chloride and 1-propanaminium, N,N′-(oxydi-2,1-ethanediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl dichloride.
In some embodiments, the cationic agent is N-(3-chloro-2-hydroxypropyl)trimethyl ammonium chloride.
In some embodiments, the cationic agent is 1-propanaminium, N,N′-(oxydi-2,1-ethanediyl)bis[3-chloro-2-hydroxy-N,N-dimethyl dichloride.
In some embodiments, the alkali is sodium hydroxide.
In some embodiments, the ratio of cationic agent to alkali in the reacting 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.
In some embodiments, the ratio of cationic treatment solution to untreated cellulosic fiber is about 10:1 to about 1:10, or about 2:1, or about 1:1.
In some embodiments, the cationic treatment solution further comprises a wetting agent.
The wetting agent can comprise, e.g., a fatty alcohol ethoxylate compound (Albaflow Conti®).
The cationic treatment solution can further comprise a defoamer.
In some embodiments, the duration of the reacting step is less than about 15 minutes, or less than about 10 minutes, or about 10-15 minutes.
The reacting step can be carried out with or without heating. In some embodiments, the reacting step is carried out without heating. In other embodiments the reacting step is carried out at a temperature of about 50° C. to about 100° C., or about 85° C. In some embodiments, the reacting step is carried out by heating the reaction to its boiling point.
In some embodiments, the reacting step is carried out in a textile machine.
In some embodiments the source of heat for the reacting step is from steam through heating coils of a textile machine.
In some embodiments, the source of heat for the reacting step is from stainless-steel cylinders of a textile machine.
In some embodiments, the source of heat is from a hot air chamber.
In some embodiments, the source of heat for the reacting step is from steam chambers of a textile machine.
In some embodiments, the reacting step is carried out without heating in a textile machine and includes a step of impregnating the cellulosic fiber with the treatment solution comprising the cationic agent and the alkali. The impregnating can be carried out in an air-free environment for 18-24 hours.
In some embodiments, the method further comprises a step of isolating a crude cationic cellulosic fiber after the reacting step. The crude cationic cellulosic fiber can be washed and neutralized with an acid (e.g., citric acid) to yield a purified cationic cellulosic fiber. In some embodiments, the washing and neutralization eliminates an undesirable amine odor.
In some embodiments, the untreated cellulosic fiber is treated with the cationic treatment solution through a yarn treatment slasher machine. The yarn treatment slasher machine can be equipped with a heating device to promote fixation.
In some embodiments, the untreated cellulosic fiber is treated with the cationic treatment solution in a package dyeing machine.
In some embodiments, the invention provides a method of preparing the cationic cellulosic fiber, by
In some embodiments, the heating is performed by conveying the padded cellulosic fiber through a heating means selected from the group consisting of a heating bath, a steam chamber, a dry can column, and a hot air chamber.
In some embodiments, the method further comprises drying the padded cellulosic fiber in an infrared predryer before the heating step.
In some embodiments, the method includes a processing step that involves, e.g., neutralizing, rinsing and drying the fixated cationic cellulosic fiber.
In some embodiments, the method further comprises sizing and winding the cationic fiber onto a loom beam for weaving.
In some embodiments, the invention further provides a method of preparing a cationic fabric from the cationic cellulosic fiber, by
In some embodiments, the cationic fabric is substantially colorless. In some embodiments, the cationic fabric is grey and/or greige.
In some embodiments, the method further comprises a step of sanforizing the cationic fabric. The cationic fabric can be sanforized to, e.g., a −3% residual shrinkage.
In some embodiments, the invention further provides a method of recycling the cationic fabric to form a regenerated cationic cellulosic fiber, by
In some embodiments, the invention provides a regenerated cationic cellulosic fiber, wherein the regenerated cationic cellulosic fiber is capable of forming a ring dyed core yarn when treated with an anionic dye, wherein the ring dyed core has a speckled appearance.
In some embodiments, the invention further provides a method of preparing a substantially colorless garment from the cationic fabric, by
In some embodiments, the shaping comprises cutting and/or sewing the cationic fabric into the substantially colorless garment.
In some embodiments, the substantially colorless garment is grey and/or greige.
In some embodiments, the invention provides a method of preparing a dyed garment from the cationic fabric, by
In some embodiments, the shaping comprises cutting and/or sewing the cationic fabric into the substantially colorless garment.
In some embodiments, the substantially colorless garment is configured such that the outside portion of the garment is facing outward prior to the reacting step.
In some embodiments, the wetting agent is a fatty alcohol ethoxylate compound (Albaflow Conti®). The wetting agent can be at a concentration of, e.g., about 0.1 to about 10 g/L, or about 0.5 g/L.
In some embodiments, the anionic dye used in the method is a direct dye, a reactive dye or an acid dye.
In some embodiments, the anionic dye comprises an SO3Na group.
In some embodiments, the anionic dye is an acid dye.
In some embodiments, the anionic dye is a direct dye.
In some embodiments, the anionic dye is a reduced sulfur dye.
In some embodiments, the anionic dye is a reactive dye.
In some embodiments, the reactive dye is a bifunctional reactive dye.
In some embodiments, the reactive dye is a high molecular weight reactive dye.
In some embodiments, the reactive dye is a bifunctional dye.
In some embodiments, the reactive dye is a vinyl sulfone dye.
In some embodiments, the anionic dye is a bifunctional dye containing at least one vinyl sulfone group.
In some embodiments, the ratio of weight of the substantially colorless garment to weight of the dye bath solution is in the range of about 1:4 to about 1:50.
In some embodiments, the dye bath solution used in the process is substantially free of sodium chloride and sodium sulphate.
In some embodiments, the dye bath solution further comprises a dispersing agent and/or a leveling agent.
In some embodiments, the dispersing agent and/or leveling agent is a lignin sulfonate.
In some embodiments, the reacting step is carried out at ambient room temperature.
In some embodiments, the reacting step is carried out at temperature in the range of about 65° C. to about 90° C., or about 85° C.
In some embodiments, the duration of the reacting step is about 5 to about 30 minutes, or about 15 minutes.
In some embodiments, the reacting step involves gradually adding the anionic dye to the dye bath solution and then reacting for about 10 minutes, after which the dye bath temperature is raised at 1° C./minute to a temperature of 85° C. and then reacted for about 15 minutes.
In some embodiments, the method further comprises a replenishing step in which the dye bath is drained after the reacting step and then replenished with a second dye bath solution comprising water, a wetting agent and anionic dye.
In some embodiments, the method further comprises a cold rinsing step of draining the dye bath solution and cold rinsing the drained garment after the reacting step. The duration of the cold rinsing step can be about, e.g., about 5 to about 20 minutes, or about 10 minutes.
In some embodiments, the colorless garment is sanforized prior to the reacting step.
In some embodiments, the dyed garment has a mélange effect and/or a denim-like appearance.
In some embodiments, the invention provides a method of producing a garment from a ring dyed core yarn, by
In some embodiments, the undyed cationic yarn is weaved into the undyed cationic fabric.
In some embodiments, the reprocessing step comprises cutting and grinding the cut-and-sew waste.
In some embodiments, the invention further provides a cationic cellulosic yarn comprising:
In some embodiments, the invention further provides an anionic dyed cellulosic yarn with
In some embodiments, the amount of anionic dye absorbed by the gradation layer is at a maximum closest to the surface layer and a minimum closest to the inner core.
As is known in the industry and prior art, approximately 99% of fabrics are created by weaving dyed yarn or dyeing the entire fabric roll. Garments are then cut-and-sewed out of dyed fabric into the finished garment. In contrast to the prior art, one example of the invention takes a yarn that can be treated using the above examples. The treated yarn can then be woven with other treated yarn or woven with untreated yarn to form a fabric. The fabric of this example is colorless or grange. The fabric can be cut-and-sewn into an uncolored finished garment, including zippers, buttons, pocket linen, and labeling. The uncolored finished garment can then be dyed using the examples above and only the treated yarn accepts the dye. All of the other features of the garment remain undyed, including the untreated yarn, zippers, buttons, pocket linen, and labeling. The cut-and-sew waste from creating the colorless finished garment can be recycled and turned back into treated yarn to form another colorless finished garment. This example allows cut-and-sewn garments to be dyed at the garment level, allowing for better inventory control and dynamic delivery of any of an almost infinite array of color pallets for the garment practically “on demand”.
The contrary example from the prior art is the production of denim. Yarn is dyed indigo blue with all of the shortcomings noted above. It is then woven with undyed yarn, in that the indigo yarn is the warp yarn and the undyed yarn is the weft yarn. After the denim fabric is created, “blue jeans” are created during the cut-and-sew process by adding the zippers, buttons, pocket linen, and labeling. The cut-and-sew waste from this process can only be again dyed blue, as the recycled fibers still have the blue dye. Further, the entire garment cannot be made colorless as the undyed yarn and zippers, buttons, pocket linen, and labeling would be dyed indigo in any process to dye the finished garment.
In some embodiments, the invention provides a method of dying garment accessories in addition to the garment, whereby garment accessories such as sewing threads and zippers are treated with the cationic reagent solution described herein so they match the color of the dyed garments after the dyeing step. Garment accessories can be dyed using the methods described herein, e.g., using mercerized cotton as the thread for the garment accessory. The garment accessories are then treated with cationic agent followed by an optional rising and neutralization step.
In some embodiments, the invention produces a garment dyed warp yarn with a ring dye core which replaces indigo or sulfur yarns in the warp of denim fabrics. In some embodiments, the invention utilizes a custom-built yarn processing machine which then produces yarn (e.g., warp yarn) having a ring dye core. The processing machine contains a plurality of component parts (e.g., individual electronic and/or steel components) and processes. Yarns treated with the machine undergo a transformation which changes the structure of the yarn such that it can be used to produce garment dyed clothing and shoes. Specifically, fabric is woven from the treated yarn and then sewn into undyed garments. The garments can then be dyed to an unlimited range of warp yarn colors with a ring dye core. Unlike the traditionally made blue jeans using indigo and/or sulfur dyes, that require large amounts of water and toxic chemicals, the yarn of the present invention eliminates that need to use indigo or sulfur dyed yarns, reduces water usage by 85% or more and eliminates use of toxic chemicals. The invention provides a means to dye warp yarns in unlimited garment dyed colors with a ring dye core that fades and abrades like indigo or sulfur dyed yarns.
In some embodiments, the invention provides a keratin fiber that is capable of forming a ring dyed core yarn when treated with an anionic dye. The anionic-dyed keratin yarn may comprise:
In some embodiments, the amount of anionic dye absorbed by the gradation layer is at a maximum closest to the surface layer and a minimum closest to the inner core.
In some embodiments, the keratin fiber contains keratin that is derived from hair, nails, feathers, horns, or claws of a mammal.
In some embodiments, the keratin is derived from wool.
In some embodiments, the invention provides a keratin fabric comprising the keratin fiber.
The keratin fiber may be substantially colorless and/or grey or greige.
In some embodiments, the keratin fabric is prepared by a process comprising the steps of:
In some embodiments, the invention provides a garment comprising the keratin fabric. The garment can be substantially colorless and/or grey or greige.
In some embodiments, the keratin-based garment is a dyed garment, e.g., a garment having a mélange effect and/or a denim like appearance.
In some embodiments, the substantially colorless garment is prepared by a process comprising the steps of:
In some embodiments, the invention provides a dyed garment, prepared by a process comprising the steps of:
In some embodiments, the invention provides a fabric comprising:
All publications, patents and patent applications including all cited art and bibliographic references cited herein are hereby incorporated by reference in their entirety for all purposes.
While many forms of the invention herein disclosed constitute presently preferred embodiments, many others are possible and further details of the preferred embodiments and other possible embodiments are not to be construed as limitations. It is understood that the terms used herein are merely descriptive rather than limiting and that various changes and many equivalents may be made without departing from the spirit or scope of the claimed invention.
The invention further includes the following aspects and embodiments:
This application claims the benefit of U.S. Ser. Nos. 63/543,611, filed Oct. 11, 2023 and 63/567,815, filed Mar. 20, 2024, the disclosures of each of which are incorporated herein by reference in their entireties.
| Number | Date | Country | |
|---|---|---|---|
| 63543611 | Oct 2023 | US | |
| 63567815 | Mar 2024 | US |
