JP2023512662A - Textile pads - steam cationization - Google Patents

Abstract

A method and system for cationizing and dyeing natural fiber-containing textiles is described. The method comprises steaming the padded textile with a base and a cationizing agent at a defined temperature range (greater than 100° C. to less than 110° C.) and for a defined period of time (1 minute to 10 minutes). A cationizing agent in the presence of a base can generate two epoxide groups. The cationization step in the presence of steam using the halogenated cationizing agents of the present invention promotes improved dyeing. [Selection figure] None

Description

The present disclosure relates to processes and systems for cationization of natural fiber-containing (eg, cotton-based) textiles that can be used to improve dye association with cationized textiles.

Textile dyeing is the process of applying pigments or dyes to textile materials such as fabrics, yarns and fibres. Desirably, the dyeing process is efficient and rapid to provide dyed textiles having the desired degree of coloration and resistance to dye fading and fading (colorfastness). Furthermore, the dyeing process and the materials used therein preferably do not adversely affect aspects of the textile such as its flexibility, durability and tactile properties such as softness, smoothness, stiffness. Various dye classes are used, depending on the textile material (eg, natural, synthetic or mixtures thereof) and the desired coloration.

Common dyes for cotton have a negative charge. However, in aqueous solutions, the surface of cotton fibers has a neutral or mildly negative charge due to the presence of hydroxyl groups in the cellulosic materials that make up cotton. Negatively charged dyes are repelled by the negatively charged cellulosic material, resulting in less uptake of the dye by the cotton. In order to dye textiles, the surface properties of cotton fibers must be modified so that the dye is not repelled. Conventional dyeing of cotton-based textiles involves the use of mixtures of salts, alkalis and dyes to associate the dye with the cotton fiber material. Salts are commonly used in dye baths to reverse the charge on cotton fibers, and alkalis are used to allow dyes to react with and associate with the induced positively charged surface of cotton fibers. used. However, these conventional processes can consume significant amounts of water, energy and chemicals, which is undesirable.

As an alternative to salt and alkali treatments, processes for modifying cotton fibers using cationic reagents are known in the art. Cationic reagents with appropriate chemical properties can react with chemical groups on cellulose to provide a permanent cationic (positive) charge on the surface of cotton fibers (“cationic cotton”). . A positive surface charge on the cotton fiber allows it to associate with a wider variety of dyes and can also allow for different color variations (eg, color depth). Cationic processes for cotton-based textiles can also consume less water, energy and chemicals, making them desirable for industrial scale operations.

One class of cationizing agents is 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (CHTAC) (see, for example, US Pat. No. 7,201,778, Hashem , M., et al., Textile Res. J., 73:1017, 2003). CHTAC can react with hydroxyl groups of cellulose in the presence of a base. In the first step, CHTAC is dechlorinated to form the reactive intermediate epoxypropyltrimethylammonium chloride (EPTAC), the epoxide groups of this compound reacting with the deprotonated hydroxyl groups of cellulose, Cationic ammonium chloride groups can thereby be covalently attached to the cellulose backbone through ether linkages. However, there is a competing reaction with water molecules that hydrolyzes the epoxide groups of EPTAC to produce the waste product 2,3-dihydroxypropyltrimethylammonium chloride (2,3-DHTAC). Therefore, the formation of 2,3-DHTAC is desirably minimized. "Batch" treatment of textiles in the presence of base and cationizing agent at low temperatures and long durations allows better reaction between cationizing agent and fiber, minimizing waste formation However, such lengthy processing steps are impractical for commercial operations.

Attempts to reduce the use of chemicals such as salts, alkalis and water to produce and dye cationic cotton have been made to improve textile dyeing. Thus, the methods and systems of the present disclosure improve cationization of textiles, such as those comprising natural fibers such as cotton, while reducing the use of chemicals in the process. The cationized textile can then be used as an improved substrate in dyeing processes to provide textiles with better color properties.

The present disclosure provides methods and systems for promoting cationization of textiles containing or derived from natural fibers such as cotton. The process of the present disclosure forms improved cationized textiles that facilitate subsequent textile dyeing and improve properties of dyed textiles, such as coloration.

Using the processes described herein, cationization of textiles can be performed in a short period of time with good results and reduced waste. Hydrolysis of the cationizing agent is minimized, improving its reaction with textiles. Subsequent dyeing of the cationized textiles provides desirable color and colorfastness. In turn, the process improves reagent usage by creating less waste, saves energy by minimizing processing time, and improves overall industrial processing efficiency. Additionally, cationizing agents of the present disclosure that are capable of generating two epoxide groups in the presence of an alkali metal hydroxide, when used in conjunction with the cationization methods described herein, monohalogenate It can provide better cationization on treated textiles compared to compounds.

In one aspect, the present disclosure provides a method for cationizing textiles comprising natural fibers or derivatives thereof. The method involves treating a textile comprising natural fibers or derivatives thereof with an alkali metal hydroxide and a cationizing agent comprising a halogenated compound capable of generating two epoxide groups in the presence of the alkali metal hydroxide. A step of treating with an aqueous solution is included. The textile is then treated in a steamy environment at a temperature above 100° C. but below 110° C. for a period of time ranging from 1 minute to 10 minutes to allow the cationizing agent to react with the textile.

In embodiments, the textile is heated to a temperature in a steam-containing environment or to a temperature in excess of one of the ranges greater than 100° C. and less than 105° C. for a period of time ranging from about 2-8 minutes.

In embodiments, the textile is heated to a temperature in a steam-containing environment or to a temperature in excess of one of the ranges greater than 100° C. and less than 104° C. for a period of time ranging from about 3-7 minutes.

In embodiments, the textile is heated to a temperature in a steam-containing environment or to a temperature in excess of one of the ranges greater than 100° C. and less than 103° C. for a period of time ranging from about 4-6 minutes.

In some embodiments, after treating the textile with the aqueous solution comprising the alkali metal hydroxide and the cationizing agent, a portion of the aqueous solution is mechanically removed from the textile.

In some embodiments, the step of treating with the aqueous solution and the step of mechanically removing are performed at a temperature of less than 35° C. and for a period of time totaling 1 minute or less.

In some embodiments, the steps of treating with the aqueous solution, mechanically removing and treating the textile with an environment comprising steam are in the range of 1 minute to 11 minutes, in the range of 1 minute to 8 minutes or 1 minute It can be run for a period of time totaling 11 minutes or less, such as in the range of ~8 minutes, which significantly enhances textile throughput while providing good cationization and incorporated nitrogen content of the textile, which in turn improves subsequent dyeing. Facilitate the process.

In some embodiments, after steaming, the textile is then neutralized with an acid-containing solution. The cationic textile can then be dyed in a composition containing the dye using the same system used for padding and steaming, or can be dyed using a different system.

Exemplary halogenated cationizing agents capable of generating two epoxide groups in the presence of an alkali metal hydroxide include, for example, bis[(3-chloro-2-hydroxypropyldialkylammonium)alkyl]ether dichloride. is a bisether halogenated dihydroxylated ammonium compound. In embodiments, the solution has a molar ratio of alkali metal hydroxide to cationizing agent greater than 1:1, such as in the range of 1.8:1 to 5:1 or 2.0:1 to 4.5:1. have. Such bis-based compounds, when used in conjunction with the methods of the present disclosure, while at the same time promoting the formation of dyed textiles having desirably bright, noticeable and long-lasting color, they: It is preferred because it can facilitate cationization and dyeing with significantly reduced production of chemicals, water, energy and wastewater.

In another aspect, the present disclosure provides a system for cationizing and dyeing textiles comprising natural fibers or derivatives thereof. The system comprises a padding bath configured to allow treatment of textiles comprising natural fibers or derivatives thereof with an aqueous solution in the padding bath, the solution comprising an alkali metal hydroxide and a cationizing agent. . The system is also configured to treat the padded textile at a temperature above 100° C. but below 110° C. for a period of time ranging from 1 minute to 10 minutes to allow the cationizing agent to react with the textile. including steam treatment equipment.

In a further embodiment, the system can also include a solution removal device for removing the aqueous solution from the padded textile after treatment in the padding bath, the system removing the textile from the padding bath in about 1 minute or less. and a conveyor device that can be moved through the solution removal device. The system may also include a neutralization bath for neutralizing the textile with an acid-containing solution. The system can include a process controller, such as a computer-based controller that can be programmed to carry out the processing methods described herein. Optionally, the system may contain a dye bath for dyeing the cationized textile.

1 is a diagram of an exemplary system for cationization and dyeing of textiles; FIG. FIG. 10 is a graph of nitrogen content on cationic cotton prepared by processing using different steaming conditions and base to cationizing agent ratios compared to a cold batch process. FIG.

The embodiments of the invention described below are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description. Rather, the embodiments are chosen and described so that those skilled in the art can appreciate and understand the principles and practices of the present invention.

All publications and patents mentioned in this specification are herein incorporated by reference. The publications and patents disclosed herein are provided for their disclosure only. Nothing herein is an admission that the inventors are not entitled to antedate any publications and/or patents, including any publications and/or patents cited herein. should not be interpreted.

The term "about" used before any numerical value in this disclosure or appended claims allows for some minor imprecision in the stated numerical value, and this imprecision may include: "About Any numerical value not preceded by the term '' can also be understood in a similar manner.

Methods and compositions of the disclosure described as "comprising" or "including" may include the recited steps and compounds, and optionally other steps and components, respectively. obtain. When methods or compositions of the disclosure are said to “consist of,” those methods or compositions have the recited steps or compounds, but do not include un-enumerated steps or compounds. The term "consisting essentially of" generally refers to a composition comprising a listed compound, and may include other non-listed compounds, but in insubstantial amounts. For example, such compositions may contain one or more other unlisted components, but greater than about 1% (by weight), greater than about 0.5% (by weight), or Not in an amount greater than about 0.1% (by weight). In compositions “consisting of” the recited components, there are no measurable amounts of other components other than the recited components, or certain steps “consisting of” the does not include steps other than

The present disclosure describes methods and systems for cationizing textiles, including natural fibers such as cotton or derivatives thereof. The cationization process can be carried out in a relatively short period of time, the process produces low levels of waste and uses minimal energy. The method and system comprise an aqueous solution (also referred to as a "padding" solution) containing an alkali metal hydroxide and a cationizing agent that is a halogenated compound capable of generating two epoxide groups in the presence of the alkali metal hydroxide. The padding can be done quickly, such as for a period of 1 minute or less, and at a temperature such as ambient temperature that does not require heating of the aqueous solution. After padding, excess solution is removed from the textile and then the textile is introduced into a steam heating device to cause reaction of the cationizing agent with the textile. Steaming is also performed fairly quickly and within a defined temperature range. In particular, the textile is treated in a steamy environment at a temperature above 100°C but below 110°C for a period of time ranging from 1 minute to 10 minutes. In some embodiments, more specific temperature and time ranges may be used.

Advantageously, good cationization is achieved without the need for long padding and reaction times (such as period of time) characteristic of cold batch padding processes. Instead, the treatment temperatures and times of the present disclosure have been found to provide good cationization of textiles while minimizing reagent loss through hydrolysis. As an added benefit of using a given steaming time and temperature, aqueous padding solutions typically require less alkali metal hydroxide than is used for monohalogenated compounds (based on reactive groups). .

The cationization method of the present disclosure leaves the textile in excellent condition for association with dyes, and the dyeing process can in turn provide good coloration of the textile. Textile dyeing can be performed using different systems or using the same systems used for padding and steaming described herein.

A "system" according to the present disclosure includes apparatus ("system components") that enable the methods of the present disclosure to be carried out. The system includes the following devices: baths for holding the processing solutions (padding bath, washing bath, neutralizing bath and/or optionally dyeing bath); textile transfer devices such as conveyors containing rollers; solution removal such as roller pairs. steam treatment equipment, including steam generators, heaters, valving; and controllers, such as computer-based operating units.

The steps of the method of the invention can be performed using continuous processes, semi-continuous processes, batch processes or combinations thereof.

One option for treating textiles is to use a continuous process. A continuous process is a flow product method used to manufacture, treat or produce an article avoiding process flow stoppages. In a continuous process, the article being processed or manufactured is in motion. In continuous processing of textiles, the textile is often in the form of a sheet that is moved through two or more processing areas (e.g., "processing zones"), and the sheet undergoes a different process within each processing area while being moved. Subjected to chemical, mechanical and/or physical processes. Movement of textiles in a continuous process can be facilitated using system devices such as textile conveyors with rollers that contact and facilitate the movement of textiles in a continuous process. A continuous process can be performed in the disclosed system described herein.

In embodiments, two or more steps of the disclosed method may be described as a continuous process. For example, in the steps of padding the textile in a solution of a base and a cationizing agent, mechanically removing a portion of the solution from the padded textile, and then steaming the textile, the textile is continuously fed through the treatment zone. , which provides predetermined treatment of the textile in motion. Other steps in the process of cationization and staining (eg washing, neutralizing and/or staining) may also be described as continuous or optionally discontinuous. FIG. 1 shows a system that can be used for continuous processing of textiles according to the disclosed method.

Semi-continuous processes may include those in which the flow product operation (continuous) is stopped and then restarted after a period of time. In some embodiments, two or more steps of the disclosed method can be described as a semi-continuous process. For example, movement of the textile can be stopped in the treatment zone for a period of time and then resumed to move the textile out of the treatment zone, depending on the desired treatment conditions. The method of the present disclosure can use a semi-continuous process in which the movement of the textile is within a steamer for a period of time and at a temperature suitable for reaction of the cationizing agent and the textile as described herein. , and textile movement is then resumed after that period to move the textile out of the steamer. A semi-continuous process can be performed with the disclosed system described herein.

Optionally, in embodiments, one or more steps in the methods of the present disclosure may be performed in a batch process. For example, prior to the processing steps of the present disclosure, or after the processing steps of the present disclosure, the textile may be modified to be configured for use in a batch process rather than a continuous process. Alterations may be made by cutting the textile and then providing a portion of the textile to be used in one or more batch processing steps. In a batch process, the system can include apparatus configured so that textiles are not automatically transferred from one apparatus to another otherwise associated with continuous process apparatus. For example, in a system that includes equipment for batch processing steps, system features such as conveyor equipment that transports textiles from one piece of equipment to another that is otherwise a continuous process, the equipment of the system used for batch processing. may not be present in at least some of the

In embodiments of the present disclosure, textiles are provided and then processed according to the steps described herein. The term "textile" refers to a flexible material comprising a network of fibers and intended to encompass all forms of textile-based articles, including woven, knit and non-woven textiles. Textiles can be in the form of sheets (fabrics) or fine strands (spun yarns). Textiles can be formed by techniques known in the art which together involve one or more processes of weaving, knitting, crocheting, felting or braiding yarns of fiber-containing materials. Exemplary textile substrates can be provided in the form of textile rolls that provide a continuous sheet of textile that can have a width of more than 1 meter and a length of up to 100 meters or more. Referring to Figure 1, the arrangement of the textile roll 10 to be treated is shown with respect to the other components of the system.

Textiles that are cationized using a cationizing agent and steam treatment according to the methods of the present disclosure include natural fibers or derivatives thereof. Natural fibers for textiles can be obtained from plants such as cotton, hemp, ramie, flax, jute, kapok, coir and bamboo. Plant raw fibers can be spun to produce long strands, which can be woven (interlaced yarns), knitted (interlaced yarns), as is known in the art of textile fabrics. can be included in textiles by e.g. In nonwovens, the plant-based fibers are not converted into yarns or yarns, but rather are directly mixed with each other or with other fibers to produce the nonwoven.

Natural fibers in textile materials may include natural polymers such as naturally occurring polysaccharides such as cellulose or cellulosic materials or chitin, or combinations thereof or derivatives thereof. Cellulose or cellulosic materials, which may include modified cellulose, as well as chitin and their derivatives, have chemicals that allow them to react with cationizing agents. Cellulose consists of repeating glucopyranose subunits displaying three hydroxyl groups on each subunit. Chitosan consists of repeating glycosamine subunits exhibiting two hydroxyl groups and one amine group on each subunit. The hydroxyl groups of these polysaccharides are reactive with hydroxide-activated cationizing agents.

Cellulosic materials also include rayon (viscose) produced from wood pulp and lyocell (eg, Tencel™), a form of rayon. Textile substrates treated according to the present disclosure may also include cellulose derivatives such as cellulose acetate or imidazolidinone-modified cellulose.

Textiles can be blends or mixtures of different materials, such as blends of natural and synthetic fibers. Blends include blends of different types of natural fibers such as wool/cotton blends, silk/cotton blends and angora/cotton blends. Animal-based materials can include collagen fibers, keratin fibers, fibroin fibers, or mixtures thereof. Other exemplary blends include cellulosic and synthetic fiber blends such as cotton/polyester blends, cotton/polyolefin blends, cotton/polyacrylonitrile blends, cotton/polyamide blends (e.g., cotton/nylon blends), and cotton/ Blends of cellulose and cellulose derivative fibers such as rayon blends are included.

When the textile comprises a blend of fibers, it preferably contains about 5% (by weight) of natural fibers or derivatives thereof such as cotton and more preferably about 25% (by weight) or more, about 35% (by weight) or more or about 40% (by weight) or more of natural fibers (eg, cellulose) or derivatives thereof. Exemplary blends include natural fibers (or derivatives thereof such as cellulose) in the range of about 5:95 to about 95:5, 25:75 to about 25:75, or 40:60 to about 60:40. Includes weight percentage of synthetic to synthetic fibers.

Woven textiles can also be described in terms of textile weight (weight/area), which is often expressed in ounces per square yard or grams per square meter. Textile weight can be influenced by the type(s) of fibers in the textile and their properties, the type of weave of the textile, and the finish of the textile. Exemplary textile weights typically range from about 50 g/m ² to about 1000 g/m ² or from about 100 g/m ² to about 750 g/m ² .

In embodiments, the process of the present disclosure utilizes bleached textiles or the process further comprises a process step of bleaching the textiles. Bleached textiles may have removed from the textile natural colors, odors and other impurities present when the fibers of the textile are in their raw (natural) form. Oxidative bleaching is typically carried out using oxidative bleaching agents such as hydrogen peroxide, sodium hypochlorite, sodium chlorite, sulfuric acid or combinations thereof. Sodium hydrosulfite is often used for reductive bleaching of textiles.

If an optional bleaching step is performed, the textile can be placed in a bleaching bath for treatment with a bleaching solution for a desired period of time. Exemplary bleaching solutions include hydrogen peroxide or sodium hypochlorite in aqueous solution at concentrations ranging from about 0.5-5.0% (by weight). After bleaching, the textile can be washed and dried.

The method of the present disclosure includes treating textiles with an aqueous treatment solution comprising an alkali metal hydroxide (base) and a cationizing agent.

Treatment of textiles with a solution containing a base and a cationizing agent can be referred to as a "padding" process in which an aqueous solution containing a treatment compound (treatment solution or padding solution) is placed in contact with the textile. Often the treatment solution is present in a container (eg, a "padding bath" or simply a "padder") in which the textile is immersed. In the padding bath, the textile can become saturated with the treatment solution. The base and cationizing agent are contacted with the textile material (and in subsequent process steps the activated cationizing agent reacts with the textile in the presence of steam). Alternatively, the aqueous treatment solution can be applied using a spray device, roller or brush. Typically, padding occurs for a short period of time, such as one minute or less.

A cationizing agent, as used herein, refers to a compound capable of associating with a textile material, such as by a chemical reaction that results in a covalent bond between the textile agent and the material. The reaction imparts a positive (cationic) charge to the textile.

Exemplary cationizing agents include halogenated and hydroxylated ammonium compounds. In the presence of a base, the compound can be dehalogenated and deprotonated to form a reactive glycidyl (epoxy) intermediate compound, which then converts the hydroxyl of the cellulosic material in the textile. can react with groups. Amine groups of chitosan-containing textiles can also be reacted with glycidyl-containing ammonium compounds to provide cationization to the textile. The methods and systems of the present disclosure use halogenated compounds that can generate two epoxide groups in the presence of an alkali metal hydroxide.

式中、Ｒ^１及びＲ^１’は独立して、メチレン、エチレン、プロピレンなどのようなＣ１－Ｃ６アルキレン基などのアルキレン（二価）基から選択され、Ｒ^２、Ｒ^２’、Ｒ^３及びＲ^３’は独立して、メチル、エチル、プロピルなどのようなＣ１－Ｃ６アルキル基などのアルキル（一価）基から選択され、Ｒ^４及びＲ^４’は独立して、Ｃ１－Ｃ６アルキレンなどのアルキレン（二価）基から選択され、Ｘ～Ｘ’’’は独立して、Ｃｌ、Ｂｒ又はＩなどのハロゲン原子から選択される。 Exemplary cationizing agents include bisether dihalogenated dihydroxylated ammonium compounds such as those of Formula I below,

wherein R ¹ and R ^1′ are independently selected from alkylene (divalent) groups such as C1-C6 alkylene groups such as methylene, ethylene, propylene, etc., and R ² , R ^2′ , R ³ and R ^3′ is independently selected from alkyl (monovalent) groups such as C1-C6 alkyl groups such as methyl, ethyl, propyl, etc., and R ⁴ and R ^4′ are independently C1-C6 alkylene, etc. and X to X''' are independently selected from halogen atoms such as Cl, Br or I.

In some embodiments, the halogenated hydroxylated ammonium compound is a bis[(3-chloro-2-hydroxypropyldialkylammonium)alkyl]ether dichloride compound. R ¹ and R ^1′ are methylene, preferably R ² , R ^2′ , R ³ and R ^3′ are independently selected from methyl, ethyl and propyl, R ⁴ and R ^4′ are Methylene, ethylene or propylene are preferred. Exemplary compounds include bis[(3-chloro-2-hydroxypropyldimethylammonium)ethyl]ether dichloride, bis[(3-chloro-2-hydroxypropyl-dimethylammonium)ethyl]ether dichloride and bis[(3 -chloro-2-hydroxypropylmethylethyl-ammonium)propyl]ether dichloride. See, for example, US Patent Application Publication No. 2015/0210627.

In embodiments, the processing solution includes the desired types and amounts of base and cationizing agent to facilitate rapid downstream processing in the steaming steps described herein. In embodiments, the concentration of cationizing agent in the aqueous treatment solution is at least about 20 g/L, but preferably no greater than 125 g/L. Preferably, the concentration of cationizing agent in the aqueous treatment solution ranges from about 40 to about 105 g/L, from about 50 to about 95 g/L, or from about 55 to about 85 g/L.

Concentrations of cationizing agents can also be expressed in terms of molarity. For dihalogenated cationizing agents, the concentration in the aqueous processing solution can be at least about 0.05 molar. Preferably, the concentration of the dihalogenated cationizing agent is from about 0.05 molar to about 0.3 molar, from about 0.1 molar to about 0.25 molar, from about 0.125 molar to about 0.225 molar, or from about 0 0.14 moles to about 0.2 moles.

Advantageously, by applying a given steaming time and temperature, the aqueous padding solution generally requires less solids reagent than is used when monohalogenated compounds are used for cationization. do. In particular, the process requires less alkali metal hydroxide, which is beneficial as it reduces waste and increases the economic efficiency of the dyeing process.

Exemplary alkali metal hydroxide bases are potassium hydroxide and sodium hydroxide. The amount of base used can be determined by the amount of cationizing agent and the steaming time and temperature. In embodiments, the concentration of base in the aqueous treatment solution is at least about 10 g/L, but preferably no greater than 40 g/L. Preferably, the concentration of base in the aqueous treatment solution ranges from about 15 g/L to about 35 g/L or from about 15 g/L to about 30 g/L. When used with a dihalogenated cationizing agent, the concentration of base in the aqueous treatment solution, when expressed in terms of molarity, can be at least about 0.25 molar or at least about 0.35 molar. Preferably, the concentration of base when a dihalogenated cationizing agent is used is from about 0.30 molar to about 1.0 molar, from about 0.35 molar to about 0.9 molar, or from about 0.40 molar to about It is in the range of 0.8 mol.

The amount of base and cationizing agent in the treatment solution can also be described with reference to the molar ratio of base to cationizing agent. In embodiments, the aqueous solution may have a molar ratio of alkali metal hydroxide to dihalogenated cationizing agent greater than about 1:1 or greater than about 1.8:1 but less than about 5:1. In preferred embodiments, the molar ratio of alkali metal hydroxide to cationizing agent is from about 1.8:1 to about 5:1, from about 2.0:1 to about 4.75:1, or from about 2.25:1 to about 4.5:1.

In some implementations, the aqueous treatment solution further comprises a thickening agent (also referred to as an "anti-migration agent"). According to the present disclosure, the use of thickeners can improve immobilization of the cationizing agent in the padded textile, which in turn improves reaction efficiency and subsequent dyeing of the cationized textile. improve. Exemplary thickeners include polyvinyl methyl ether (e.g., having an average molecular weight of about 100,000), sodium alginate, Gaur gum, carboxymethylcellulose (CMC), low molecular weight cellulose ethers, polyethylene glycol (e.g., having an average molecular weight in the range of 8,000 to 10,000), polyvinylcaprolactam and acrylic polymers, acrylic polymers being preferred thickeners. Preferred thickeners should not interfere with dyes, should not cause loss of color vibrancy, should have sufficient liquid stability, should not cause any difficulties in handling, should be good at room temperature It should have good solubility and should provide good efficacy in small amounts. In embodiments, a thickening agent is provided in the padding bath to provide a viscosity in the range of about 50 to about 350 cP. In exemplary embodiments, thickeners may be used in amounts ranging from about 2% to about 20% (by weight) or from about 5% to about 10% (by weight) in the aqueous padding solution.

Aqueous padding solutions are generally maintained at a temperature(s) of 35° C. or less. Preferably, the aqueous padding solution is at a temperature in the range of about 15°C to about 27°C or about 18°C to about 25°C.

In some exemplary modes of practice, the method is a continuous process in which the textile is fed into a treatment bath, the textile is moved through the bath and then exits the bath. In embodiments, the padding step can be performed quickly. Referring to FIG. 1, a sheet of textile 12 advances from a textile roll 10 into a padding bath 20 holding a treatment solution 22 comprising a cationizing agent and a base. The padding bath 20 includes a set of rollers (24a-24c) to facilitate movement and positioning of the advancing textile sheet in the processing solution 22. The residence time in the padding bath (“padding time”) is defined by the time that a particular portion of the textile enters the bath and then ends when the particular portion exits the padding bath. Typically this is greater than 0.5 seconds, greater than 1 second or greater than 2 seconds and generally less than 1 minute, no greater than about 45 seconds or no greater than about 30 seconds. Exemplary padding times range from 1 second to 1 minute, 1 second to 45 seconds, 1 second to 30 seconds, 1 second to 20 seconds, 1 second to 15 seconds, 1 second to 10 seconds, or 2 seconds to 5 seconds. is.

In embodiments, the residence time of the textile in the padding bath can be determined by machine speed as well as other aspects of the system. For example, the residence time of the textile in the processing area can be known based on the speed at which the textile conveyor device of the system moves the textile through the processing area and the length of the travel path through the processing area. In an exemplary system, the textile conveyor apparatus moves the textile through at least the padding bath at a speed ranging from about 20 meters/minute to about 50 meters/minute. Exemplary lengths of travel paths through the padding bath can range from about 0.5 meters to about 5 meters, or from about 1 meter to about 4 meters.

The padding process can cause the textile to become "soaked" or "saturated" with the treatment solution. In some implementations, excess treatment solution can be removed from the textile and returned to the padding bath once the textile exits the bath. Referring to FIG. 1, the textile is advanced from the treatment solution 22 through a pair of rollers (26a, 26b) which apply pressure to the padded textile to remove excess treatment solution, which is a padding bath. 20. However, sufficient treatment solution is maintained in the textile to provide an amount of base and cationizing agent to react with the textile in the subsequent steaming step.

A padded textile can be described in terms of the amount of aqueous treatment solution present in the textile (the "effective concentration"). For example, a padded textile can be referred to in terms of "wet pick-up" which is the amount (weight) of treatment solution present in the textile divided by the weight of the dry textile prior to padding. Generally, the padding step provides a wet pickup of the processing solution of greater than about 50%. Preferably, the padding step provides a wet pickup of processing solution in the range of about 60% to about 80%. In an exemplary scenario, if the cationizing agent is present in the padding bath at 100 g/L and there is 70% wet pick-up, the effective concentration of cationizing agent in the textile is 70 g/L or 7%.

Generally, the padding process and removal of any excess treatment solution from the saturated textile can be carried out rather quickly, which facilitates the overall process of cationization and dyeing of the textile.

After padding the textile, it is introduced into a device that adds steam energy to the padded textile and promotes reaction and bonding of the cationizing agent to the textile. Referring to FIG. 1, the sheet of textile 12 advances from the roller pair (26a, 26b) through the opening 32 and into the steam treatment device 30. As shown in FIG. Steaming apparatus 30 includes a set of rollers (34a-34e) on which the textile can be supported and moved through the steam chamber. The apparatus also includes a steam generator (not shown) including a water container and a heating element capable of heating a volume of water for boiling to produce steam introduced through a conduit (not shown). can have The chamber may also have heating elements (not shown) to maintain the vapor-containing atmosphere at the desired temperature according to the present disclosure. The steaming step is performed for a short period of time in a well-defined temperature range.

Steam processes can be described in terms of steam density within a steam chamber. The density of the vapor depends on the temperature of the vapor or the size of its container or its pressure. At 100° C. at normal atmospheric pressure, steam (ie, dry steam) has a density of 0.0006 grams per cubic centimeter (600 g/m ³ ). In the method of the present disclosure, the vapor density within the chamber is at least 0.0006 g/cm ³ . However, steam chambers typically contain dry steam in which all water molecules are in the gaseous state, and also wet steam in which some of the water molecules lose their energy and condense into water droplets in the air. . Optionally, the steam used in the methods of the present disclosure may be referred to as being from the dry fraction of wet steam. For example, if the water content in the steam is 5% by weight, the steam is said to be 95% dry with a dry fraction of 0.95. By comparison, note that under normal atmospheric conditions, up to about 30 grams of water vapor can exist in a volume of 1 cubic meter of air at a temperature of about 35°C.

Upon introduction into the steam chamber, the padded textile is rapidly heated to the steam temperature set for the device. Generally, the textile is heated to the desired temperature for a short period of time, such as less than 15 seconds or less than 10 seconds. Once the textile reaches the desired temperature, it can be moved through the steam chamber.

The textile is heated to a temperature in the steam chamber or to a temperature of at least 100° C. but less than 110° C. and then for a period ranging from 1 minute to 10 minutes to react the cationizing agent with the textile. is held at this temperature for a certain period of time.

Preferably, the textile is heated to a temperature in the steam chamber or greater than 100°C to about 109°C, greater than 100°C to about 108°C, greater than 100°C to about 107°C, greater than 100°C to about 106°C, greater than 100°C to about 105°C. °C, from greater than 100 °C to about 104 °C, or from greater than 100 °C to about 103 °C. Preferably, the textile is dried from about 1 to about 10 minutes, from about 1 to about 9 minutes, from about 2 to about 8 minutes, from about 2 to about 7 minutes, from about 3 to about 7 minutes, from about 3 to about 6 minutes, or from about 4 minutes. Treated at a temperature in any one of these ranges in steam for a period of time ranging from to about 6 minutes.

Exemplary heating temperatures and treatment times are such that the textile is heated to a temperature in the steam chamber or to a temperature in the range of greater than 100° C. to approximately 105° C. for a period of time ranging from about 2 to about 8 minutes. is the case.

Another exemplary heating temperature and treatment time is that the textile is heated to a temperature in the steam chamber or to a temperature in the range of greater than 100° C. to about 104° C. for a period of time ranging from about 3 to about 7 minutes. is the case.

Another exemplary heating temperature and treatment time is that the textile is heated to a temperature in the steam chamber or to a temperature in the range of greater than 100° C. to about 103° C. for a period of time ranging from about 4 to about 6 minutes. is the case.

The steaming temperatures and times of the present disclosure allow rapid reaction of the cationizing agent with reactive chemicals while minimizing hydrolysis of the cationizing agent that would otherwise render the cationizing agent non-functional. can promote

Optionally, the treated textile can be described in terms of efficiency of reaction of the cationizing agent with the textile. Reaction efficiency can be expressed in terms of the amount of cationizing agent reacted per unit weight of textile (eg, mmoles of cationizing agent per gram of textile material). Reaction efficiency (degree of cationization) can be determined by the amount of nitrogen content of the textile as imparted by the cationizing agent. For example, the process of the present disclosure provides at least about 0.075 mmol of nitrogen (from cationizing agent) per gram of textile. More typically, there is at least about 0.085 mmol, at least about 0.09 mmol, or at least about 0.095 mmol of nitrogen (from the cationizing agent) per gram of textile. Determination of the reaction of the cationizing agent can be determined by the Kjeldahl method or the combustion method (e.g. Schwarzinger, C., et al. (2002) Monatshefte fur Chemie 133:1-17, or Ma, W., et al. (2017) Molecules , 22:2235) by analyzing the added ammonium groups to the textile.

After steaming the cationized textile, it can be washed with a hot aqueous solution. The hot water wash removes at least a portion of any unreacted or hydrolyzed cationizing agent, base and/or other optional components (e.g., thickening agents) carried over from the padding bath. be able to. For example, in a continuous process, steamed textiles can exit steamer 30 through opening 36 and be fed to hot water bath 40 . Hot water bath 40 includes a set of rollers (44a-44e) to facilitate movement and positioning of the advancing textile sheet in hot water.

Hot aqueous solutions may have a pH in the range of 6-8. The temperature of the hot water bath preferably ranges from about 70°C to about 90°C or even more preferably from about 75°C to about 85°C. The cationized textile can be maintained in the hot water bath for a period of time less than 20 minutes, less than 15 minutes, such as a time ranging from about 5 minutes to 15 minutes. In a continuous process, the textile can be moved through the bath, such as rollers in the bath, and then the textile can exit the bath after the desired washing period. The washed textile can be transferred to the neutralization bath without removing the water from the textile.

After the cationized textile has been hot washed, it can be neutralized by treatment with an acid. The acid can react with any remaining base present in the textile, thereby neutralizing the cationized textile. For example, in a continuous process, referring to FIG. 1, the washed cationized textile can exit a hot water bath 40, such as by passing through a pair of rollers (not shown) to remove the hot water solution. , can be processed mechanically and then fed to a neutralization bath 50 containing an aqueous composition 50 containing an acid. Neutralization bath 50 may include a set of rollers (54a-54e) to facilitate movement and positioning of the advancing textile sheet in the acid-containing solution of the bath.

The acid-containing solution can have an exemplary pH ranging from about 4 to about 5. For example, acid solutions can be formed using weak acids such as acetic acid, citric acid or oxalic acid, or combinations thereof. The amount of acid can depend on the type of acid used, but an exemplary acid is acetic acid at concentrations ranging from about 1 to about 2 grams per liter. The acid treatment solution is generally maintained at a temperature(s) of 35°C or less. Preferably, the acid treatment solution is at a temperature in the range of about 15°C to about 27°C or about 18°C to about 25°C.

The cationized textile can be maintained in the acid treatment solution for a period of time less than 20 minutes, less than 15 minutes, such as a time ranging from about 5 minutes to 15 minutes. In a continuous process, the textile can be moved through the acidizing solution, such as rollers, in a bath, and then the textile can exit the acidizing solution after the desired washing period. As such, the staining step and staining apparatus may or may not be part of the disclosed methods and systems.

The systems and methods of the present disclosure may optionally include one or more steps of cold or hot water washing between post neutralization/acid treatments.

After the cationized textile is neutralized, it can be dyed by treatment in a dye solution. The dyeing process can be carried out using the same system as the padding bath and steamer, or can be carried out in a separate system separate from the padding bath and steamer. If the dyeing process is performed using a different system, such as in a dyeing facility at a different location than the facility with the padding/steaming system, the cationized textile can be transported to that facility and dyed.

For the purpose of discussing the steps of dyeing textiles, reference is made to Figure 1 which shows a system with a dyeing bath. For example, in a continuous process, the neutralized cationized textile can exit the neutralization bath 50 and be mechanically processed, such as by passing through a pair of rollers (not shown) to remove any excess acid solution. It can be treated systematically and then fed into a dye bath 60 containing a composition having a dye. Dye bath 60 may include a set of rollers (64a-64e) to facilitate movement and positioning of the advancing textile sheet in the dye solution.

Cationized textiles can accept a variety of dyes, thus offering good flexibility for color provision. Cationized textiles can provide improved dye association through chemical interaction between the positively charged quaternized nitrogen of the textile binding cationizing agent and, for example, the anionic groups of the anionic dye. However, cationized textiles can also accommodate other dye types that associate the dye with the textile in a manner independent of the textile binding cationizing agent.

The "dyeing" process imparts color to textiles, and "dye", as described herein, refers to any substance that provides color to textiles, which may also include pigments. Dyes can be associated with textile fibers by chemical reaction, absorption, dispersion, or a combination thereof. Dyes typically differ in their resistance to sunlight, perspiration, washing, gases and alkalis, their affinity for different fibers, their reaction to cleaning agents and processes, and their solubility and method of application. Exemplary types of dyes that can be used to color cationic textiles made using the methods and systems of the present disclosure include natural dyes, basic (cationic) dyes, direct (substantially) dyes. , sulfur dyes, pigment dyes, vat dyes, reactive dyes and acid dyes.

Reactive dyes are capable of reacting with one or more chemical groups of the textile fibre. Reactive dyes can be applied from alkaline or neutral solutions, which are then alkalized in a separate process. Heat treatment can also be used during dyeing to generate different shades. After dyeing, the textile can be washed with soap to remove any unfixed dye. Reactive dyes can be used on cationic textiles, including cellulose fibers, and those including blends of wool, silk, nylon and acrylic.

Direct dyes can directly color cellulose fibers without the need for the use of mordants (dye fixatives). Direct dyes can be used on cationic textiles, including cellulose fibers, as well as those containing blends of wool, silk, nylon, rayon, and the like.

Sulfur dyes are water insoluble and are made soluble using reducing agents and alkaline pH (eg caustic soda and sodium sulfide). Dyeing is done at high temperatures with large amounts of salt so that the color penetrates the fibres. After dyeing, the textile is oxidized by exposure to air or by using chemicals to provide the desired shade. Excess dyes and chemicals can be removed by thorough washing. Sulfur dyes are fast to light, wash and perspiration and are most often used on cotton and linen.

Vat dyes are insoluble in water and are typically made soluble by reduction in alkaline solutions, allowing them to be fixed to textile fibres. Subsequent oxidation or exposure to air restores the dye to its insoluble form. An exemplary vat dye is indigo. Vat dyes are the most fast dyes for cotton, linen and rayon. Vat dyes are commonly used with mordants to dye other textiles such as wool, nylon, polyester, acrylic and modacrylic.

Pigments are not strictly dyes, but are still used to color textiles such as cotton, wool and other man-made fibres, due to their excellent lightfastness. Pigments are typically fixed to textile fibers using resins. After dyeing, the textile is exposed to high temperatures. In some embodiments, the dyeing step according to the present disclosure can use pigments to color the cationized textile. Natural dyes obtained from natural sources such as plant, animal or mineral sources can be used with cationized textiles. Direct printing is the most common approach for applying color patterns on textiles. When done on colored textiles it is known as overprinting. The desired pattern is produced by pressing the dye onto the textile in paste form. To prepare the printing paste, the thickener is added to a limited amount of water and the dye is dissolved therein. In the past, starch was the preferred thickening agent for printing. More recently, gums or alginates derived from seaweed are preferred as they allow better color penetration and are easier to clean. Most pigment printing is done without thickeners, as mixing of resin, solvent and water causes thickening.

Some dyes used to dye cationic textiles include "reactive" or anionic dyes. Reactive anionic dyes may contain one or more anionic groups such as sulfonate or carboxylate groups. For example, an anionic dye can contain one or more sodium sulfonate (--SO ₃ Na) groups. One or more anionic groups may be present in the dye molecule which absorbs light within the visible spectrum and may have at least one chromophore/color-bearing group with a conjugated system. Commonly used anionic dyes include those based on azo chemistry, anthraquinone chemistry and triphenylmethane chemistry. Azo dyes are chemically characterized by the group RN=NR', where R and R' generally comprise an aryl group, with various chemical substituents attached to the aryl group. . Other anionic dyes include those with nitro, azine and quinoline chemistries. Acid dyes are a class of anionic dyes that may contain acid groups such as carboxylic acid groups, sulfonic acid groups or phosphoric acid groups. Anionic dyes that can be used in the methods of the present disclosure are described in Aspland, J.; R. , (1997) Textile Dyeing and Coloration, American Association of Textile Chemists and Colorists, AATCC, Knutson, L.; (1986) Synthetic Dyes for Natural Fiber, Interweave Press; Revised edition. Examples include "Reactive Blue 19", "Direct Blue 71", "Acid Blue 62", "Reactive Red ME4BL", etc., preceded or followed by color names and numbers and/or letters. , "Direct" and "Acid".

In some embodiments, the concentration of the anionic dye in the dyeing solution ranges from about 0.001 g/L to about 5.0 g/L, from about 0.01 to about 2 g/L, with more concentrated The dye solution provides a more intense dye color to the textile. In embodiments, the anionic dye solution is generally maintained at a temperature in the range of about 30°C to about 80°C. Staining can be performed for a desired period of time, such as in the range of about 30 minutes to about 60 minutes. Referring to FIG. 1, after dyeing the textile may be washed (not shown) and then wound around rollers 72 .

Operation of one or more portions of the system is controlled using a process controller (not shown), such as a computer-based controller that can be programmed to carry out the processing methods as described herein. be able to.

Example 1
Rapid padding of cotton fabric - steam cationization and dyeing Bleached cotton fabric (A4 size) was treated with the cationizing agent bis[(3-chloro-2-hydroxypropyldimethylammonium)ethyl]ether dichloride (ECOFAST™ Pure; Dow ), annotated as bis-CHPDMAEEDC) and sodium hydroxide. The concentrations of bis-CHPDMAEEDC and NaOH base are listed in Table 1.

The solution was at ambient temperature (20° C.) and the fabric remained in the solution for about 2-3 seconds before being removed. The soaked fabric was then passed through two rollers at 70% markings to squeeze excess solution from the fabric. Therefore, the effective concentration of cationizing agent on the fabric was 49 g/L (0.119 mol).

This was followed by steam treatment of the padded fabric at a temperature of 102° C. for various time periods (5, 10, 15, 20 minutes).

As a control, cationizing agent and base (70 gpl of bis-CHPDMAEEDC and 20 gpl of NaOH) were padded onto A4 cotton cloth and then batch reacted at low temperature (25° C.) for a period of 14 hours.

After steaming, the cationized fabric is washed with hot water at a temperature of 80° C. for 10 minutes, then the washed fabric is washed with acetic acid (1.5 g/NaOH concentration) for 10 minutes at ambient conditions (temperature of 30° C.). L) was neutralized in a solution containing After cationization, the nitrogen content on the fabric was evaluated by the combustion method.

Dyeing was carried out by placing 2 gm of cationic cotton in a dye composition containing 3% Reactofix Red ME4BL dye solution and 15 g/L sodium carbonate to improve fixation and performance properties. The dye solution had a temperature of 60° C. and the fabric remained in the solution for 30 minutes. This was followed by a washing process of cold wash and neutralization, hot wash at 60° C. for 10 minutes, and then cold wash. The results of rapid steaming were compared and normalized against a cotton fabric prepared as a control (Table 1 and Figure 2).

Surprisingly, the above results show that using a bis-cationizing agent, limited amounts of base, short steaming times and steam temperatures close to 100° C. results in good dyeing (with less residual color in the bath). ), which showed good nitrogen content on cotton and good color strength.

Claims (19)

A method for cationizing textiles comprising natural fibers or derivatives thereof, comprising:
A textile comprising natural fibers or derivatives thereof is treated with an aqueous solution comprising an alkali metal hydroxide and a cationizing agent comprising a halogenated compound capable of generating two epoxide groups in the presence of said alkali metal hydroxide. to process;
treating the textile in an environment comprising steam at a temperature in the range of greater than 100° C. to less than 110° C. for a period of time ranging from 1 minute to 10 minutes to allow the cationizing agent to react with the fabric. including, method. 2. The method of claim 1, wherein the cationizing agent is a bisether halogenated dihydroxylated ammonium compound. The cationizing agent has the formula

wherein R ¹ and R ^1′ are independently selected from alkylene groups, R ² , R ^2′ , R ³ and R ^3′ are independently selected from alkyl groups, R ⁴ and R ^4′ is independently selected from alkylene groups such as C1-C6 alkylene, and X to X''' are independently selected from halogen atoms. R ¹ and R ^1′ are independently selected from methylene, ethylene and propylene; R ² , R ^2′ , R ³ and R ^3′ are independently selected from methyl, ethyl and ^propyl ; 4. The method of claim 3, wherein R ^4' is independently selected from C1-C6 alkylene. 5. The method of claim 4, wherein the cationizing agent is bis[(3-chloro-2-hydroxypropyl-dialkylammonium)alkyl]ether dichloride. at a temperature in the range of greater than 100°C to less than 107°C, greater than 100°C to less than 106°C, greater than 100°C to less than 105°C, greater than 100°C to less than 104°C, or greater than 100°C to less than 103°C , is treated in steam. the textile for a period of time ranging from 1 to 10 minutes, from about 1 to 9 minutes, from about 2 to 8 minutes, from about 2 to 7 minutes, from about 3 to 7 minutes, from about 3 to 6 minutes, or from about 4 to 6 minutes; A method according to any one of claims 1 to 6, wherein the process is carried out in steam. A method according to any preceding claim, comprising mechanically removing a portion of the aqueous solution from the fabric after treating with the aqueous solution. 9. The method of claim 8, wherein the aqueous solution treatment and the mechanical removal are performed at one or more temperatures below 35[deg.]C and for a total period of 1 minute or less. A total of 45 seconds or less, 30 seconds or less, 1 second to 1 minute, 1 second to 45 seconds, 1 second to 30 seconds, 1 second to 20 seconds, 1 10. The method of claim 9, wherein the method is performed for a period of time ranging from seconds to 15 seconds, 1 second to 10 seconds, or 2 seconds to 5 seconds. the step of treating with the aqueous solution, the step of mechanically removing, and the step of treating the fabric in a steam-containing environment for a total of 11 minutes or less, 10 minutes or less, 9 minutes or less, 8 minutes or less, 7 minutes or less, or Executed for a fixed period of 6 minutes or less, or for a fixed period ranging from 1 minute to 11 minutes, 1 minute to 10 minutes, 1 minute to 9 minutes, 1 minute to 8 minutes, 1 minute to 7 minutes, or 1 minute to 6 minutes The method according to any one of claims 8 to 10, wherein 12. The method of any one of claims 1-11, wherein the aqueous solution has a molar ratio of the alkali metal hydroxide to the cationizing agent greater than 1:1. 13. The method of claim 12, wherein the molar ratio of the alkali metal hydroxide to the cationizing agent is within the range of 1.8:1 to 5:1 or 2.0:1 to 4.5:1. Method. The method of any one of claims 1-13, wherein the aqueous solution further comprises a thickening agent. 15. The method of any one of claims 1-14, further comprising neutralizing the fabric in an acid-containing solution after treating with steam. The method of any one of claims 1-15, further comprising dyeing the fabric with a composition comprising a dye. A system for cationizing and dyeing textiles comprising natural fibers or derivatives thereof, the method comprising:
A natural fiber configured to hold an aqueous solution comprising an alkali metal hydroxide and a cationizing agent comprising a halogenated compound capable of generating two epoxide groups in the presence of said alkali metal hydroxide. or a padding bath for treating textiles containing a derivative thereof,
The fabric may be treated in an environment containing steam to react the cationizing agent with the fabric at a temperature in the range of greater than 100° C. to less than 110° C. for a period of time ranging from 1 minute to 10 minutes. A system, comprising: a processor; a roller mechanism for mechanically removing a portion of the aqueous solution from the fabric;
a neutralization bath for neutralizing the fabric in an acid-containing solution;
18. The system of claim 17, further comprising one or more of: 19. The method of claim 17 or 18, further comprising a process controller that enables said treatment with said aqueous solution and said mechanical removal at one or more temperatures below 35[deg.]C and for a period of time totaling no more than 1 minute. system.

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