TR2022010651T2 - DENIM TRANSFER DYEING METHOD WITH REACTIVE DYES - Google Patents

Abstract

The present invention relates to a method for transfer dyeing denim with reactive dyes comprising: 1- desizing of raw denim to obtain raw denim; 2- applying a dyeing accelerator liquid to a front side of the raw denim to obtain a wet coated front side; 3- printing a reactive dye ink onto a first set of distributor rollers or distribution blanket belts using a first set of printing plate rollers of a transfer dyeing apparatus; 4- To bring the wet coated front side obtained in step 2 into tight fit and pressure contact with the first set of distributor rollers or distribution blanket belts in step 3 to transfer the reactive dye ink from a first set of distributor rollers and to ensure the coloring of the front side of the raw denim drying; 5- applying dyeing accelerator liquid to a back side of the raw denim to obtain a wet coated back side; 6- printing the reactive dye ink onto a second set of distributing rollers or distribution blanket belt using a second set of printing plate rollers of the transfer dyeing apparatus; 7- With a wet coating obtained in step 5, bring the back side into tight fit and pressure contact with the second set of distributor rollers or distribution blanket belts in step 6 to transfer the reactive dye ink from the second set of distributor rollers or distribution blanket belt and the raw denim drying to color the back side; and 8) finishing the raw denim on the colored front and back side to obtain a denim product.

Description

DESCRIPTION METHOD OF DENIM TRANSFER DYEING WITH REACTIVE DYEING Technical Field of the Invention The present invention relates to printing and dyeing technology in the textile industry and, in particular, to a method for transfer dyeing of denim with reactive dyes. The method can significantly increase the affinity between reactive dyes and denim fiber, reduce the amount of remaining dye, increase the utilization degree of dyes, and meanwhile promote energy saving and consumption reduction. Background of the Invention Classic denim is a thick thread twill created by 3/1 right hand twill weaving using pure cotton indigo dyed threads as warp and undyed pure cotton white threads as weft. With the development of textile technology, in addition to cotton fiber, which is the main raw material of denim, there are other fibers, including natural fibers such as hemp, ramie, linen, silk, wool, viscose, tencel and modal, and chemical fibers such as polyester, nylon, acrylic and spandex. The manufacturing process of denim is unique. It is a product woven from indigo dyed and finished warp threads. It includes indigo dyeing, rope dyeing, sheet dyeing and skein dyeing for denim's warp threads. The first two are performed after sizing, and the last one is performed before sizing. Classic denim is usually dyed with indigo dye and sulfur dyes. Indigo dye is the most commonly used dye in the denim dyeing process, and approximately 60,000 tons of indigo dye are used in the world every year. Indigo dye, belonging to a vat dye, is blue powder, insoluble in water or general organic solvents and soluble in concentrated sulfuric acid, molten phenol, hot aniline or concentrated acetic acid solution. The melting point of indigo dye is 390-392°C. When heated to 170°C, the indigo dye produces fuchsia sublimated gas and does not decompose. Indigo is a water-soluble Iuko body in an alkaline solution of sodium hydrosulfite, and Iuko acid is a white substance that is slightly soluble in water. Compared to common vat dyes, indigo has a low dyeing rate, which will result in inadequate dyeing. In addition, due to the poor bleeding performance of indigo dye, the thread dyed with indigo dye will be ring dyed, that is, there is a distinct white core in the center of the thread. Sulfur dyes are organic compounds containing nitro and amino groups and have a structure similar to that of vat dyes. They undergo chemical reduction to form the water-soluble Iuko body with affinity for Lierre, thereby dyeing Lierre, and then undergo an oxidation process to bind tightly to Lierre. Both indigo dye and sulfur dyes require the use of large amounts of inorganic salts and also require large amounts of water for extensive washing after dyeing to reduce residual dyes on the textile. In general, wastewater from the washing process of common denim processing plants contains large amounts of inorganic salts and dyes, which increases the chemical oxygen demand (COD) of the wastewater. It is reported that COD in the effluent is up to approximately 2,200-2,800 mg/L, and the suspended solid chromaticity is approximately 1,500-1,800 times. Therefore, the current denim dyeing process is not environmentally friendly at all. As environmental protection policies become more stringent, the cost of production will constantly increase. Additionally, the dyeing process is unstable and is greatly affected by seasons and the environment. A slight change in conditions will cause changes in color and tone, resulting in poor reproducibility. In addition, commonly used commercial indigo dyes are difficult to bind with deep and bright colors, and the color fastness of commonly used commercial indigo dyes is low, especially color fastness to rubbing and washing, and can easily stain other textiles during washing. In recent years, with the diversification of people's living demands, the market has begun to seek multi-color environmentally friendly denim printing and dyeing, and some colorful denim dyed with reactive dyes have emerged. Reactive dyes, also called chemically reactive dyes, are anionic dyes whose molecules contain chemically active groups and react with cotton, wool and other fibers in an aqueous solution to form bonded dyes together. Reactive dyes are very popular due to their good viability, ease of use and good color fastness. However, reactive dyes are very prone to hydrolysis when subjected to covalent bonding with fibers, leading to low dye uptake and degree of fixation. In the traditional dyeing process, a large amount of inorganic salt is usually required to prevent the accumulation of negative charges on the fiber surface and improve the dye absorption performance. However, this will result in wastewater with high salt content, thus affecting the environment or causing wastewater treatment problem. In light of the above problems in the prior art, the inventors developed a method to transfer dye denim with reactive dyes. The method can significantly increase the affinity between reactive dyes and denim fibers, thus stabilizing the dyeing quality, increasing fastness to washing, fastness to rubbing and fastness to weather conditions, reducing the amount of dye residue, increasing the degree of use, saving energy and reducing consumption and reducing environmental pressure. encourages reduction. Figures Helping to Explain the Invention Figure 1 is a general axial end view of an anilox roller pretreatment device used in steps 2 and 5 in the method of the present invention. Figures 2a and 2b are a general schematic view of a transfer dyeing apparatus and a schematic view of a transfer dyeing recorder used in steps 3, 4, 6 and 7, respectively, in the method of the present invention. Figures 3a and 3b are a nuclear magnetic resonance spectrum and an infrared spectrum, respectively, of a dye accelerator used in example 1. Figure 4 is the infrared spectrum of the fluorine-containing bifunctional reactive dyes used in example 2. Figures 5a and 5b are a nuclear magnetic resonance spectrum and an infrared spectrum, respectively, of a dye promoter used in example 3. Figure 6 is the infrared spectrum of the fluorine-containing bifunctional reactive dyes used in example 4. Reference Numbers to Help Explain the Invention 1. Main roller 2. Anilox roller 3. Squeegee blade 4. Receiver tank. Painting recorder 7. Drying oven. Central roller 12. Frame 13. Variable frequency motor. Online central roller cleaning system. Textile 40. Guide roller 501. Dye recorder body frame 502. Mounting block 503. Eccentric sleeve 504. Rotary arm shaft 506. Pusher roller 508. Rotary arm 509. Actuator 510. Ink jet assembly 511. Full template printing plate roller 512. Distributor roller 516. Connecting rod 517. Pressure lock 900. Image detection unit Disclosure of the Invention In one aspect, the present invention provides a method for transfer dyeing denim with reactive dyes, comprising: 1) destorage of raw denim to obtain raw denim; 2) applying a dyeing accelerator liquid to a front side of the raw denim to obtain a wet-coated front side; 3) printing a reactive dye ink onto a first set of distributing rollers or dispensing blanket belts using a first set of printing plate rollers of a transfer dyeing apparatus; 4) bring the wet coated front side obtained in step 2 into tight fit and pressure contact with the first set of distribution rollers or distribution blanket belts in step 3 to transfer the reactive dye ink from the first set of distribution rollers or distribution blanket belts and the front side of the raw denim drying for coloring; ) applying dyeing accelerator liquid to a backside of raw denim to obtain a wet-coated backside; 6) printing the reactive dye ink onto a second set of distributing rollers or dispensing blanket belt using a second set of printing plate rollers of the transfer dyeing apparatus; 7) with a wet coating obtained in step 5, bring the back side into tight fit and pressure contact with the second set of distributor rollers or distribution blanket belts in step 6 to transfer the reactive dye ink and the raw denim drying to color the back side; and 8) finishing raw denim with colored front and back sides to obtain a denim product. The resulting disassembly in step 1 is known in the art. Cotton fiber symbionts, raw cotton pigments, found in raw denim have a negative effect on the transfer dyeing effect and stability of denim, and desizing eliminates this negative effect, improves the water absorption of denim and benefits dye uptake and permeability. For example, raw denim can be washed in a stripping enzyme liquid at about 40-80°C and preferably about 50-60°C for about 2-5 hours and preferably about 3-4 hours in water at 60°C or higher, e.g. It is washed at approximately 90°C, then washed with water at room temperature and dried to obtain raw denim. The degrading enzyme liquid is known in the art. An exemplary stripping enzyme liquid may preferably contain about 0.1-0.5%. It contains 0.2-0.3% non-ionic surfactant and deionized water based on the total weight of the stripping enzyme liquid. The desorbing enzyme is known in the art and is commercially available, including, for example, medium temperature oi-amylase or broad temperature oi-amylase. Chlorine-containing alkali metal salt, e.g. NaCl, etc. Non-ionic surfactant, such as fatty alcohol polyoxyethylene ethers, sorbitan fatty acid esters, polyoxyethylene-polyoxypropylene block polymers, polyoxyethylene compounds, are known in the art. In addition to the above ingredients, the stripping enzyme liquid may also contain additives common to the art, which include, for example, preservatives (e.g., benzoic acid, sorbic acid, dehydroacetic acid or diacetic acid preservatives), activators (e.g., sodium chloride or calcium chloride), but It is not limited to these, the application in Step 2 is known in the art. For example, the dyeing accelerator fluid can be applied to the front of raw denim in an anilox roller coating fashion using an anilox roller pretreatment device shown in FIG. Dyeing accelerator liquid is used in an amount such that the curl expression of raw denim is 20% or more, for example 25-50%. Anilox rolls (2) may include laser etched chrome plated anilox rolls (2) or number of lines. The process of applying the dyeing accelerator liquid on raw denim in steps 2 and 5 will be described with reference to FIG. The pretreatment device shown in FIG. 1 includes a pressure-bearing main roller (1), and a woven fabric is wrapped around the pressure-bearing main roller (1). The two sides of the pressure-bearing main roller (1) mainly consist of an anilox roller (2), a closed doctor blade (3), a receiving tank (4) and the coating head device containing an anilox roller feeding mechanism, respectively. The left and right anilox roller coating head devices have the same structure. The main roller (1) carrying pressure is fixed to a frame (12). One side of each anioox roller (2) is opposite the pressure-carrying main roller (1) and the other side is equipped with a closed doctor blade (3). The outer diameter of the pressure-carrying main roller (1) is larger than the outer diameter of the anilox roller (2). The pressure-carrying main roller (1) and the anilox roller (2) are arranged horizontally and their axes are in a straight line. During sizing, two anioox rollers (2) are brought into contact with the pressure-bearing main roller (1) under a suitable pressure by means of a roller. The pressure-carrying main roller (1) is driven to rotate by a pressure-carrying main roller (1) motor. Meanwhile, one anioox roller (2) motor does not work and two anioox rollers (2) are driven to rotate by the rotation of the pressure-carrying main roller (1). Meanwhile, a one-way bearing of the anilox roller (2) ensures the rotation of the pressure-carrying main roller (1) to the anilox roller (2). At the same time, the closed doctor blade (3) is contacted/separated from the anioox roller (2) by means of a doctor blade (3) drive mechanism. In case of contact, the doctor blade (3) body, the cylinder body and a corresponding sealing element move together to form a closed chamber. Using a pump, the required dyeing accelerator liquid can be injected into the closed chamber through an injection port located on the closed scraper blade. In addition, the closed doctor blade (3) is also equipped with a closable discharge port that facilitates the emptying of the dyeing accelerator liquid in the compartment. As the pressure-carrying main roller (1) and the anilox rollers (2) rotate, the dyeing supporting liquid in the chamber is applied to the textile (20) through the anilox rollers (2). When production is suspended, the two anilox rollers (2) are separated from the main roller (1) that carries the pressure by means of the roller. Meanwhile, the anioox roller (2) is driven to rotate by the anioox roller (2) motor, which facilitates the rapid cleaning of the anioox roller (2). Dyeing accelerator liquid is disclosed in Application No. 3, the entire contents of which are incorporated herein by reference. Specifically, the dyeing promoter composition includes 3-5% of a dyeing accelerator, a leveling agent, and agents, modifiers, salts, dispersants, solvents, and the like known in the art, based on the total weight of the dyeing promoter composition. Preferably, the balance of the dye accelerator composition is a dispersant or solvent, such as water. The dye promoter is a bifunctional quaternary ammonium salt compound having an ethylsulfonyl group and a monohalo-s-triazinyl group, with the structural formula (1) shown below: Meoîîmoâcirg- CY2_î Nar' \\,ýN\ where M, H or a the alkali metal ion is preferably a Na or K ion; Y each independently represents H, halogen or linear or branched 01-12 alkyl, preferably H; X each independently represents halogen, preferably Cl or F, more preferably Cl; and R1 and Rg are each selected equally or differently from the following quaternary ammonium groups: or (R3)3N -R4-, wherein Rg each independently represents linear or branched O1-12 alkyl, preferably methyl, ethyl or propyl. where R4 represents linear or branched O1-12 alkylene, preferably ethylene, propylene or butylene, and R0 optionally represents one or more (e.g., 1, 2, 3 or 4) substituents selected from halogen or C1_8 alkyl on a benzene ring. represents the doer. In the context of the present application, the term "alkali metal" refers to a metal element of Group 1A of the periodic table, including Li, Na, K, etc., preferably Na or K. In the context of the present application, the term "alkyl" preferably represents a linear or branched alkyl having 1-12, preferably 1-8 or 1-4 carbon atoms and may be substituted by one or more halogens such as H, F, Cl or Br on the carbon atom. . In a preferred embodiment, alkyl represents unsubstituted O1-8 alkyl, more preferably O1-4 alkyl such as methyl, ethyl, propyl or butyl. In the context of the present application, the term "halogen" preferably includes F, Cl and Br, and more preferably represents Cl. The group R0 optionally represents one or more substituents selected from halogen or O1-8 alkyl on the benzene ring. In a preferred embodiment, each benzene ring in formula (1) has no substituent R0, that is, the benzene ring is unsubstituted. According to the present invention, in the preferred compound of formula (1): M is Na or K; Y represents H; X represents Cl; Rg each independently represents linear or branched O1-8 alkyl, more preferably C1-8 alkyl, particularly preferably methyl or ethyl; R4 represents linear or branched C1-8 alkaline, more preferably O2-6 alkylene, particularly preferably propylene; and/or the benzene ring does not contain the Ro substituent. The compound of formula (I) as described above can be prepared by a method comprising the following steps: (1) m-phenylhydroxyalkyl trialkyl ammonium salt, p-phenylhydroxyalkyl trialkyl ammonium salt, or hydroxyalkyl optionally substituted with one or more Ro groups One or more 10 trialkyl ammonium salts selected from the trialkyl ammonium salt undergo a ring-closing reaction under alkaline conditions to obtain the corresponding epoxy derivatives. (2) The epoxy derivatives obtained in step (1) are subjected to amination to obtain the corresponding amino derivatives. (3) The amino derivatives obtained in step (2) are reacted with 1,3,5-trihalo-s-triazine and p-(p-sulphatoethylsulfonyl)aniline optionally substituted with one or more Ro groups. The binder generally serves as a dispersion medium, which may consist, for example, of vegetable oil, mineral oil, an organic solvent, various natural and synthetic resins, and a small amount of wax. In a preferred embodiment, the binder may be selected from sodium alginate, guar gum, synthetic tragacanth gum, cellulose and derivatives thereof, starch and derivatives thereof, acrylic acid or crotonic acid multipolymers and derivatives thereof, and mixtures thereof. The surfactant may be selected from polyvinylpyrrolidone, polyoxyethylene alkyl amine, fatty alcohol polyoxyethylene ether, polysiloxane ether, or mixtures thereof. The straightening agent may be selected from alkali metal alkyl sulfonates such as alkyl sodium sulfonate or alkali metal fatty alcohol sulfates such as higher fatty alcohol sodium sulfate or fatty alcohol polyoxyethylene or polyoxypropylene or mixtures thereof. The alkaline agent may be selected from amine compounds and alkali metal hydroxides such as sodium hydroxide or potassium hydroxide. The inventors demonstrate that the bifunctional quaternary ammonium salt with both monohalo-s-triazinyl and ethylsulfonyl groups has excellent fixation reaction properties for cotton fibers and serves as a dyeing accelerator to modify raw denim prior to dyeing, while having significant ecological advantages over the traditional dyeing method. They found that it is. For example, using the compound of formula (I) of the present invention as a dyeing accelerator can greatly reduce or eliminate the need for conventional salt as a dyeing accelerator, while the dyeability of fiber fabric can be maintained or even improved. Therefore, cost, purification and disposal difficulties related to salt addition can be eliminated. In addition, after treatment with the dyeing accelerator of the present invention, the dyes can be completely bound to the cotton fiber tissue to realize high visible color yield, thus maximizing the utilization of dyes and significantly reducing the usage of dyes. In addition, the resulting textile 20 can be dyed homogeneously and has good color fastness, thus reducing the need for fixing alkaline agents. Therefore, in a preferred embodiment of the present invention, the preferred dyeing promoter composition may also contain other suitable salts such as sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate. However, as one of the beneficial effects of the present invention, in a preferred embodiment, the use of those alkaline agents that are likely to cause pollution (e.g., alkali metal hydroxides and alkaline agents selected from amine compounds, including alkylamines such as organic triethylamine) in the dyeing accelerator composition can be reduced ( for example, 5%, 2%, 1% or even lower than 0.5%, depending on the weight of the supporting composition) and their use may be avoided, or organic ammonium salts other than the quaternary ammonium salt compound of formula (1) may also be avoided. The transfer dyeing apparatus used in step 3 is known in the art. For example, the transfer dyeing apparatus may be used to print reactive dye ink onto a first set of distributing rollers or dispensing blanket belts using a first set of printing plate rollers in the apparatus. Printing platen rollers may include gravure platen rollers, flexographic platen rollers, or rotary screens. One material of the surface of the distribution roller 512 or distribution blanket belt is a layer of rubber coating 3-15 mm thick. Rubber is polyurethane rubber, nitrile-butadiene rubber, styrene-butadiene rubber, chloroprene rubber, chlorosulfonated polyethylene rubber, ethylene-propylene rubber or similar with a surface hardness of 45-90°Sh. All these10 rubbers have a low surface tension. For example, the critical surface tension of polyurethane rubber is about 29, the critical surface tension of butyl rubber is about 27, and the surface tension of styrene-butadiene rubber is about 48. Therefore, during transfer dyeing of raw denim, such viscosity and surface tension are particularly suitable for applying reactive dye ink to distributing rollers 512 or distributing blanket belts, thus improving processability. The transfer dyeing apparatus in steps 3, 4, 6 and 7 will be described below with reference to FIG. The transfer dyeing apparatus essentially includes a central roller (10) and at least one dyeing recorder (5). The dyeing unit has a satellite structure and at least one dyeing recorder (5) shares a central roller (10) as a counter pressure roller. A frame (12) is fixedly connected to the central roller (10) by means of a bearing. The central roller (10) can be driven to rotate by a variable frequency motor (13). The central roller (10) may be a hard material roller coated with rubber on the surface. At least one (e.g. 2-8, e.g. 6 in FIG. 2a) dyeing recorder (5) is distributed on the peripheral outer surface of the central roller (10). Each of the dyeing recording devices (5) is independently provided with a driving force to advance towards the central roller (10) by a corresponding driving device, for example a pushing roller (506). The pusher cylinder (506) is mounted on the body of each of the painting recorders (5), for example, on the painting recorder body frame (501). Optionally, the transfer dyeing apparatus may also include a guide roller (40). At least one guide roller (40) is placed next to each of the inlet and outlet where the textile to be dyed (20) is in contact with the central roller (10). The guide roller (40) directs the textile (20) into or out of a pressurized section located between the central roller (10) and the dyeing recorder (5). A drying oven (7) may be located between the dyeing recorders (5) and used to allow ink to dry after printing, thus preventing smearing and color contamination between multiple recordings. The transfer dyeing apparatus may also include an online central roller cleaning system (15) arranged in a non-pressurized section between the central roller (10) and the dyeing recorder (5). The online central roller cleaning system (15) includes a cleaning device, a squeegee and an oven. After the surface of the central roller (10) is cleaned by the cleaning device, the water on the surface of the central roller (10) is scraped off by the wiper blade and the central roller (10) is dried in the oven, thus ensuring continuous cyclic use of the central roller (10). The cleaning device may include a spray head and a hairbrush. The transfer dyeing apparatus may also include a high resolution image detection unit 900. The high resolution image detection unit 900 may be a high speed camera. The high-speed camera captures a pattern formation after staining and sends the image to a central control unit for treatment. An image signal is then generated on the liquid crystal display for an operator to monitor the quality of the print job in real time, thus increasing efficiency. Figure 2b shows a dyeing recorder 5 of the transfer dyeing apparatus according to this example of the present application. The dyeing register device 5 may include the above-mentioned pusher device (e.g., pusher roller 506), an ink jet assembly 510, a full-stencil printing platen roller 511, a distributor roller 512, and a press assembly. The ink jet assembly (510), full-stencil printing platen roller (511), distributor roller (512) and press assembly are mounted on the dye recorder body frame (501). The distributor roller (512) is located between the full template platen roller (511) and the central roller (10) and may be in contact with the full template platen roller (511). The corresponding spindle ends of the distributor roller (512) and the full template printing plate roller (511) can be mounted on a mounting block (502) within the dye recorder body frame (501). The mounting block (502) can slide on a slide rail within the paint recorder body frame (501). Thus, under the driving movement of the pusher roller (506), the assembly block (502) moves towards the central roller (10), in this case, the distributor roller (512) moves the textile (20) to be dyed on the central roller (10) of the distributor roller (512). It reaches a position where it is in contact with. Here, the delivery roller (506) and also the distributor roller (512) reaches a position where it is in contact with the textile (20) to be dyed on the central roller (10). The pressing device can be used to provide adjustable pressure to press the distributor roller (512) against the full template platen roller (511). The pressing device is used to adjust the amount of ink to control the color difference, and the pressure is mainly used to remove the ink from the cells of the anilox roller (2). In the example shown, the pressing assembly includes an actuator 509 and an eccentric sleeve 503. The actuator 509 includes a cylinder body and a piston rod. The cylinder body can be axially connected to the mounting block (502). Actuator 509 may be hydraulic, pneumatic, or electric. If the actuator 509 is hydraulic or pneumatic, the extension length of the piston rod can be adjusted by regulating the fluid pressure in the chamber of the cylinder body. The actuator 509 may be a servo actuator, such as a servo electric cylinder. The pressing assembly may also include a rotating arm 508 and a connecting rod 516. The rotating arm (508) can be axially connected to the mounting block (502) via a rotating arm shaft (504). The rotary arm (508) includes a first end and a second end. The first end of the rotary arm (508) can be axially connected to the extension end of the piston rod of the actuator (509) via an axis pin. The second end of the rotary arm (508) can be pivotally connected to one end of the connecting rod (516) via an axis pin. The other end of the connecting rod (516) can be connected axially to the eccentric sleeve (503). The dyeing recorder 5 may also include a pressure lock 517 to lock the pressure between the distributor roller 512 and the full pattern printing platen roller 511, thus preventing slight fluctuations in the pressure value caused by the uneven surface of the textile 20 during production. is prevented. The pressure cabinet may include a variable length component. One end of the component can be axially connected to the eccentric sleeve (503) and the other end can be axially fixed to the mounting block (502). Reactive dye ink consists of chitosan and 2-18%, preferably 4-13%, reactive dyes with two reactive groups, based on the total weight of the reactive dye ink. Guar gum is a galactomannan gum, and galactomannan is a neutral polysaccharide gum, a plant polysaccharide gum widely used in industry. An aqueous solution of galactomannan gum is a pseudoplastic liquid whose macromolecule has a tangled network structure in a natural state. As a common form, guar gum contains as structural units a main chain formed by linking (1-4)-ß-D-mannose and a side chain consisting of a single α-D-galactose and connected to the main chain by a (1-6) linkage. . From the perspective of the whole molecule, galactoses are distributed randomly on the main chain, but mostly in groups of two or three. Due to different sources, the molecular weight and ratio of monosaccharides of guar gum are different from other galactomannans. The molecular weight of guar gum can generally be about 0.5-3 million, such as 1-2 million, and the ratio of mannose to galactose can be approximately 1.2-2.5:1, such as approximately 1.5-2:1. Guar gum derivatives suitable for the present invention are not particularly limited as long as they are water-soluble cationic guar gum derivatives or water-soluble nonionic guar gum derivatives. In one embodiment, guar gum derivatives are selected from guar gum having a degree of substitution DS of 0.15 or 0.25. Such guar gum derivatives include oxidized guar gum, such as hydroxylated or carboxylated guar gum, such as hydroxypropyl guar gum or carboxymethyl guar gum. Guar gum or its derivatives as a paste are very important for rheological properties, permeability and leveling properties, have excellent compatibility with the fluorine-containing bifunctional reactive dyes of the present invention and have excellent solidifying effect when printing on the rubber surface of the dispensing roller 512 or dispensing blanket belt. Additionally, the content of guar gum or its derivatives is also important in the reactive dye ink of the present invention. If the content of guar gum or its derivatives is too low, the dyes will have strong permeability and poor surface color yield, and the color will not be bright enough, and if the content is too high, the dyes will have poor leveling properties and poor fastness after washing. Chitosan, the only alkaline polysaccharide found so far, has many amino groups in its molecule. The inventors have found that chitosan can absorb a cotton to form a film layer, thereby improving the dye uptake of the cotton textile (20). The inventors have also found that chitosan, when combined with guar gum or its derivatives, has a synergistic effect, especially in adjusting the rheological properties of dye ink. The dye ink of the present invention is used primarily in a transfer dyeing process. It is hoped that leveling of painting based on less paste and higher ink capacity will also be considered. Therefore, appropriate rheological properties are a very important point for both the upper limit and the leveling of transfer dyeing. In general, in the present invention, chitosan when combined with guar gum or its derivatives can further improve color absorbency, have color deepening and brightening effects while reducing the amount of dye, and adjust the rheological properties of dye ink to better suit the transfer dyeing process. The paste slurry can be prepared simply by mixing guar gum or guar gum derivatives and chitosan in water at a certain weight ratio. For example, add water by weight or deionized water, stir the mixture sufficiently for about 1-2 hours until sufficient dissolution is achieved, add 0.5-1.5 wt% chitosan, add distilled water or deionized water to 100%, and give the mixture complete dissolution and uniform color. It is mixed until it is obtained, thus transfer dyeing paste slurry is obtained. Reactive dyes having two reactive groups can be those known in the art, for example, HE dyes containing bis-monochloro-s-triazinyl reactive groups developed by lCl or reactive dyes of the Drimarene XN or Sumifix Supra series from Clariant. The two reactive groups monochloro-s-triazinyl and vinylsulfonyl developed by SUMlTOMO (Japan) or Shanghai No. ME dyes developed by 8 Member Chemical Plant or Basilen FM dyes developed by BASF or Megafix B type dyes developed by Shanghai Matex Chemicals Co may be included in this scope. In a preferred embodiment, reactive dyes having two reactive groups are bifunctional reactive dyes containing the entire content. Specifically, fluorine-containing bifunctional reactive dyes have a vinylsulfonyl group or vinylsulfonyl precursor group and a monofluoro-s-triazinyl group and can be expressed by the following formula: where D is a dye intermediate, B is a single bond or a monofluoro-s-triazinyl group, such as -NH- is the coupling group and Re is a reactive Dye intermediate containing a group containing monofluoro-s-triazinyl and not containing chloro-s-triazinyl and a group containing vinylsulfonyl (-SOgCH=CH2) or vinylsulfonyl precursor, respectively, and is known in the art, e.g. azo, anthraquinone, phthalocyanine and other dye parent compounds or structural modifications thereof may also be referred to as a dye chromophore. These parent compounds, or forms with reactive groups attached to them, are often commercially available, such as Cibacron F reactive dyes from Huntsman, or Liyuansu FL reactive dyes from Color Root, or Levafix EN reactive dyes (whose parents are linked by the monofluoro-s-triazinyl group). ) is within this scope. Such reactive dyes containing two reactive groups (vinylsulfonyl or vinylsulfonyl precursor and halo-s-triazinyl) or methods for their preparation are known and commercially available. Such reactive dyes have been used in dyeing fiber fabrics. Common reactive dyes of this type usually contain two reactive groups, vinylsulfonyl and monochloro-s-triazinyl. However, the inventors found that if the chlorine in the s-triazinyl reactive group structure10 in the dye molecule is replaced by fluorine, the stability of the dyed fibers can be greatly increased when the dye is used for printing and dyeing, and the fiber bond is more stable than dyes containing a monochloro-s-triazinyl reactive group. preferably a substituted or unsubstituted monofluoro-s-triazinyl group, more preferably an unsubstituted one, shown as formula (III) below. The monofluoro-s-triazinyl group can be used as a reactive group. The Vinylsulfonyl precursor group may be any group that can be converted to a Vinylsulfonyl group under suitable media and conditions, such as alkaline conditions, and may be, for example, during dyeing, a Vinylsulfonyl precursor-containing group or preferably the ester ethylsulfonyl-containing group shown below as formula (1V). M-R1- CY2 -CYz-S- F (iii) cn› (lV) where M is H or an alkali metal ion, preferably Na or K; R1 is an ester group selected from sulfate, carboxylate and phosphate, preferably a sulfate group (-OSOg-); R2 is H, hydroxyl, alkyl, alkoxy, amino or mono- or dissubstituted amino; and Y each independently represents H, halogen or linear or branched 01-12 alkyl, preferably H. A known example of a compound commonly used to introduce a group containing a vinylvinylsulfonyl precursor is a para-ester (or p-(p-sulphatoethylsulfonyl)aniline) or derivatives or analogs thereof. In the context of the present application, the term "alkali metal" refers to a metal element of Group 1A of the periodic table, including Li, Na, K, etc., preferably Na or K. In the context of the present application, the term "alkyl" preferably represents linear or branched alkyl having 1-12, preferably 1-8 carbon atoms, which may be substituted by one or more halogens such as H, F, Cl or Br on the carbon atom. In a preferred embodiment, alkyl represents unsubstituted C1-8 alkyl, more preferably O1-4 alkyl such as methyl, ethyl, propyl or butyl. The term "alkoxy" refers to alkyloxy where alkyl is as defined above. In the context of the present application, the term "aryl" preferably represents an aromatic group having 5-12, preferably 6-10 carbon atoms, preferably phenyl or alkylphenyl. Single or double substituted amino groups are in principle not limited and are substituted amino groups or hydroxyalkyl substituted amino groups known in the field of dyes, including, for example, alkyl, alkoxy, aryl, amido, sulfamido, amidoalkyl, sulfamidoalkyl. In addition to the combination of specific paste slurry and specific bifunctional reactive dyes described above, the reactive dye ink may also include, but is not limited to, a rare earth drier, resist agent, dispersant, surface tension regulator and water balance. Rare earth dryer can increase the drying speed and improve the production efficiency of waterborne reactive dye ink, and rare earth has the effect of helping color deepening and brightening for reactive dyes. The rare earth desiccant can be selected from carboxylates of rare earth elements, for example rare earth isoctoates or rare earth naphthenates. The fineness of the rare earth desiccant is not limited and can be, for example, S10 microns, S8 microns or 5 microns. Rare earth drier can be used in an amount of 0.2-3%, for example 0.5-1%, based on the total weight of the dye ink. Resistance is used to control the dyeing process. It is a substance that can prevent dyes from coloring and forming patterns on a fiber textile (20) or during the printing and dyeing process. Examples of suitable resist agents include Resist H (based primarily on sodium metanitrobenzene sulfonate) and Resist H (based primarily on ammonium hydrazinobenzenesulfonate). The resist agent can be used at a rate of 0.2-3% and preferably 0.5-1%, depending on the total weight of the dye ink. The dispersant may be selected, for example, from methylene naphthalenesulfonic acid dispersants, phenol aldehyde condensate sulfonate dispersants, or fatty alcohol polyoxyethylene ether silane dispersants. The dispersant can be used in an amount of 1-10%, preferably 1.5-7%, more preferably 2-5%, based on the total weight of the dye ink. The surface tension regulator is not particularly limited and can, for example, be a non-ionic surfactant, such as BYK-DYNWET 800 from BYK (Germany), Efka 3570N from BASF or Hydropalat 140 from Cognis. Surface tension regulator can be used in the amount of paint. An appropriate amount of surface tension regulator can be added to adjust the surface tension of the reactive dye ink to be less than the critical surface tension of the distributor roller 512 or distribution blanket belt in the transfer dyeing apparatus, so that the ink is clearly printed on the surface of the distributor roller 512 or distribution blanket belt. Reactive dye ink can be prepared by homogeneously mixing and integrating fluorine-containing bifunctional reactive dyes as described above with the paste slurry and other optional ingredients and additives. In one embodiment, fluorine-containing bifunctional reactive dyes can be mixed with optional other water-soluble ingredients and additives, and then optionally the mixture is filtered and the filtered mixture is added to the paste slurry. If necessary, bifunctional reactive dyes containing fluorine can be made into a paste with water in a container beforehand. The viscosity of reactive dye ink is about 50-4,000 mPa.s, preferably about. The reactive dye ink of the present invention generally uses the surface of a rubber blanket belt or a rubber roller as a temporary transfer printing carrier. All rubbers have low surface tension. For example, the critical surface tension of polyurethane rubber is about 29, the critical surface tension of butyl rubber is about 27, and the surface tension of styrene-butadiene rubber is about 48. Therefore, during transfer dyeing of raw denim, such viscosity and surface tension are particularly suitable for applying the ink to the distributor rollers 512 or distribution blanket belts, thus improving the processability. In particular, compared with indigo dyeing, sulfur dyeing or vat dyeing, the reactive dye ink of the present invention can significantly reduce the pollution when dyeing raw denim and improve the poor color and tone stability and poor dyeing repeatability in dyeing raw denim with commercially available reactive dyes. The contact process in step 4 is known in the art and can be carried out under the conditions of linear pressure of 10-80 kg/cm and speed of -60 m/min. The drying process is also known in the art, for example drying can be carried out with hot air or infrared radiation. The application operation in step 5 and the dyeing accelerator liquid used here are the same as in step 2. For example, the dyeing accelerator liquid can be applied to the backside of raw denim in an anilox roller coating fashion using second anilox rollers (2) in the anilox roller pretreatment device to obtain a backside with a wet coating. The color of the reactive dye ink used in step 6 may be the same or different from the color of the reactive dye ink used in step 3; This corresponds to the dyeing request of the same color on both sides or different colors on both sides and different colors can be obtained by changing a D dye parent in the reactive dye molecule known to those skilled in the art. The transfer dyeing apparatus used here is also known in the art and may be the same as that used in step 3. The contact and drying processes in step 7 are the same as in step 4. The finishing operation involved in step 8 is known in the art, including, for example, fixing, washing, curing and the like. Fixation may include steam fixation or oven fixation. The washing process usually consists of washing in cold water, washing with hot water (40-50°C) to remove salts, alkalis and unfixed dyes, soaping, washing with hot water (70-95°C) to further remove a dye solution bound to the fibers and washing with cold water. C, <10 minutes). A setting machine is then used for drying and hardening. Optionally, before soaping, neutralization can be carried out in an acetic acid bath to prevent the dyes from being hydrolyzed during soaping and thus avoid the adverse effects of residual alkaline electrolytes. The feature of the method for transfer dyeing denim in the present invention is the use of a combination of specific dyeing supporting liquid and specific reactive dye ink. Using dyeing accelerator liquid to modify raw denim can effectively improve the affinity between fibers and reactive dyes, so that a deep chroma can be achieved without salt during dyeing, which greatly reduces the pollution caused by washing. Accepted reactive dye ink includes reactive dyes having two reactive groups, vinylsulfonyl and monofluoro-s-triazinyl. While the vinylsulfonyl group undergoes nucleophilic addition with the fibers, the monofluoro-s-triazinyl group also partially participates in the reaction. Due to the synergistic effect of the two reactive groups, the reactivity of the entire dye is increased and a stable dye-fiber bond is formed, resulting in a higher color fastness. At the same time, reactive dye ink has low requirements for dyeing temperature and amounts of alkaline agents and dyeing promoters, has good trichromatic compatibility and good reproducibility, and has a significantly higher degree of dye uptake and fixation than single dyes with a single reactive group. The method of the present invention adopts a transfer dyeing method that is completely different from the traditional denim production process. In this dyeing method, only the surface of the denim is dyed, and there is no need to fill the inside of the fibers and the invisible parts with dyes, thus dyeing is carried out on demand. This leads to the beneficial effects of proper dye intake and a high degree of fixation, significantly reducing the amount of dye and consequently water consumption, thus producing a significantly reduced amount of waste. The present invention will be further described by way of examples. It should be noted that these examples should not be considered limiting of the present invention. The test methods in the examples are as follows: Degree of fixation: It is tested according to the method of determining the degree of fixation of the print in GB/T 2391-2014 "Determination of the Degree of Fixation of Reactive Dyes". Dry rubbing fastness and wet rubbing fastness: GB/T 3920-2008 "Textile - They are tested according to "Color Fastness Test - Color Fastness to Rubbing". Lightfastness and color fastness to soaping: They are tested according to GB/T 14575-2009 "Textile - Color Fastness Test - Comprehensive Color Fastness". Example 1: Pure cotton herringbone transfer dyed raw denim from twill denim fabric. Weight: 10 OZ; Width: 58-60 inches; Content: 100% cotton. Denim fabric is transfer dyed by a method that includes the following steps: 1- Desoldering: at 50°C, raw denim, They were charged in a stripping enzyme broth containing a balance of 0.6% medium temperature α-amylase, 0.6% NaCl, 0.2% fatty alcohol polyoxyethylene ether, and deionized water (to 100%) for 3 h, followed by Washed with 90°C hot water, washed with water at room temperature and dried to obtain raw denim to be printed. 2- Application of dyeing accelerator liquid to the front side: Dyeing accelerator liquid was applied to one front side of the raw denim, laser-engraved chrome-plated anilox with a line count of 200 lines/cm in a line. It was applied evenly as anilox roller coating using rollers (2). The anilox roller pretreatment device shown in FIG. 1 was put into operation to obtain a wet coated front. The dye accelerator liquid contains 3% a dye accelerator, 5% guar gum, 1% polyvinylpyrrolidone, 0.5% alkyl sodium sulfonate, 8% a 1:1 mole ratio mixture of sodium carbonate and sodium bicarbonate, and the remainder deionized water (to 100%). much). The dyeing promoter is shown as the formula below and its nuclear magnetic resonance spectrum and infrared spectrum are shown in FIG. 3a and 3b: NaOýISiiýOICHZ- GHz-î N-i/l \|_N\ where X is Cl, R1 and R2 are respectively: The above dyeing promoter It was synthesized as follows: Under room temperature and stirring conditions, 1 part 40% NaOH aqueous solution by molar mass was added dropwise to each of 1 part m-phenylhydroxymethyl trimethylammonium hydrochloride by molar mass (purchased from Sigma-Aldrich, analytically pure ) and 1 part by molar mass of hydroxypropyl trimethylammonium hydrochloride (purchased from Sigma-Aldrich, analytically pure) were placed in the reactors. After completion of the dropwise addition, the reaction was continued for 30-60 minutes. The NaCl produced in the reaction was filtered and the pH of the solution was adjusted to 6.5–7 with hydrochloric acid, thus obtaining the corresponding epoxy derivatives, respectively. A 32% excess of concentrated ammonia water was then added dropwise to each of two reactors containing fresh epoxy derivatives. After completion of the dropwise addition, the reaction continued for 3-4 hours. Excess ammonia was then removed under vacuum at 80°C to obtain two corresponding amino derivatives in a yield of about 85% or above. Then, under a uniform stirring environment at 0-5°C, the solution of 1,3,5-monochloro-s-triazine and p-(ß-sulphatoethylsulfonyl)aniline in acetone gradually converted into the above m-phenylhydroxymethyl trimethylammonium hydrochloride amino derivatives. was added drop by drop. The pH of the reaction was adjusted and controlled to 6.5 with a Na 2 O 3 aqueous solution as necessary until the reaction was completed and a precursor product was obtained. Meanwhile, the addition of the Na2CO3 aqueous solution was stopped and the pH of the solution remained at 6.5. The reaction system containing the precursor was heated to 35-40°C and amino derivatives of hydroxypropyl trimethylammonium hydrochloride were added dropwise with stirring. The pH of the reaction was also adjusted and controlled to 6.5 with a Na2CO3 aqueous solution until the reaction was completed and the denim fabric dyeing promoter was obtained. Meanwhile, the addition of the Na2CO3 aqueous solution was stopped and the pH of the solution remained at 6.5. 3) Delivery of reactive dye ink: The first set of printing plate rollers of a transfer dyeing apparatus in Figure 2 was used to print a reactive dye ink onto a first set of distributing rollers. The formulation of reactive dye ink is as follows: Composition % weight Slurry paste 50% Reactive dyes 12% Rare earth drier (rare earth naphthenates, fineness 55 05% micron) Resistance S 1% Dispersant (methylene naphthalenesulfonic acid dispersant) 4% Surface tension regulator (BYK) from BYK-DYNWET 1% Purified water to 100% The paste slurry was prepared as follows: 5% by weight (based on the total weight of the paste slurry) of hydroxypropyl guar gum with a degree of substitution of DS 2 0.15 was placed in a container, 70% by weight distilled water or Deionized water was added and the mixture was stirred sufficiently for 2 hours. After sufficient dissolution was achieved, 1% chitosan by weight was added, distilled water or deionized water was added up to 100% and mixing continued until complete dissolution and homogeneous color were achieved. Reactive dyes, lCl Procion Blue HERD are dual-function reactive dyes produced by Procion Blue HERD.The reactive dye ink was prepared as follows: first, about 2% by weight (a small amount) of cold water and the above reactive dyes were added to a container and made into a paste. Then, a mixed solution of resist S, dispersant and surface tension regulator, dissolved according to the amounts shown in the table above, was added, approximately 85°C warm water was added to dissolve the reactive dyes sufficiently, at a level of 15% by weight. The mixture was filtered, the filtrate was added to the prepared paste slurry, 100% water by weight was added, and the mixture was mixed uniformly to obtain reactive dye ink. The viscosity of the resulting reactive dye ink was 900 mPa.s and the surface tension was 27 mN/m. 4) Front side painting: The front side with the wet coating obtained in step 2 was brought into tight fit and contact with the first set of distribution rollers or distribution blanket belts in step 3 under a linear pressure of 80 kg/cm and reactive Dye ink was transferred to the front of the raw denim through the first set of distributor rollers or distribution blanket belts, and drying was carried out under infrared irradiation to color the front of the raw denim. ) Application of dyeing accelerator liquid to the backside: The same dyeing accelerator liquid as in step 2 above was applied uniformly as a coating to one backside of the raw denim using laser-etched chrome-plated secondary anilox rollers (2) to obtain a wet-coated backside. This was achieved with anilox rollers (2) with a line count of 200 lines/cm in the anilox roller pre-treatment device in FIGURE 1. 6) Delivery of reactive dye ink: The same reactive dye ink as in step 3 was printed on a second set of dispensing rollers or dispensing blanket belt using a second set of printing plate rollers of the transfer dyeing apparatus in FIG. 7) Backside painting: The backside with a wet coating obtained in step 5 was brought into tight fit and contact under a linear pressure of 10 kg/cm with the second set of distribution rollers or distribution blanket belts in step 6'. In order to transfer the reactive dye ink from the second set of distributor rollers or distribution blanket belts to the back side of the raw denim, drying was carried out under infrared irradiation to realize the coloring of the back side of the raw denim. 8) Final process: Raw denim was subjected to steam fixation process at 102°C for 10 minutes, washed (washed with cold water - 50°C, washed with hot water for 10 minutes - soaped (95°C, 10 minutes) - washed with hot water (95°C). C, 5 min)-washed with cold water), then a fixer was used for drying and fixation. According to the above methods, the obtained pure cotton stained denim was determined to have a dry rubbing fastness of Grade 4-5, a wet rubbing fastness of Grade 3.5-4, and a light fastness of Grade 5, and the fixation degree of the dye ink was 85%. Example 2: Transfer dyeing of pure cotton baleen/twill denim fabric In Example 2, the same steps as in Example 1 were used to transfer pure cotton denim fabric except that the Procion Blue HERD reactive dyes were replaced with bifunctional reactive dyes containing fluorine. Fluoride Bifunctional reactive dyes containing were prepared as follows: 1- One mole of 1-amino-8-naphthol-3,6-disulfonic acid was placed in deionized water and beaten for 1 hour, adjusting the pH of the slurry to 6.5+/-0.2 for dissolution. NaOH was used for and the mixture was cooled to 0°C-5°C and stored for later use 2- One mole filter cake of purified Cibacron F reactive dyes Cibacron Blue FR from Huntsman and 1-amino from step 1) The -8-naphthoI-3,6-disulfonic acid solution was mixed and NaHCO › was added dropwise until the pH was 4.5±+/-0.2. At 30°C-40°C, the mixture was stirred at low speed to react for 3 hours, an end point was determined with an amino reagent, and the resulting liquid was cooled to 10°C and stored for later use. After mixing 1 part per mole of p-(p-sulphatoethylsulfonyl)aniline and beating for 1 hour, ice was added to cool the slurry to 0-10°C. 1 part mole of concentrated hydrochloric acid was added, 1 part mole of NaNO2 was slowly added dropwise to obtain a 30% solution, diazotization was performed, and Cl starch test paper was used for detection to ensure a slight excess of nitrous acid. After the dropwise addition was completed, the mixture was stirred at 0.5°C for 1 hour and excess nitrous acid was removed with sulfamic acid. The liquid obtained in step 3 was slowly added to the liquid obtained in step 2 or cooled to 10°C. The pH was adjusted to 6.5 ± 0.2 with NaHCO ›, and the reaction was carried out by stirring for 4 hours to obtain the fluorine-containing bifunctional reactive dyes used in this example. The infrared spectrum of a dried sample of fluorine-containing bifunctional reactive dyes is shown in FIGURE 4. According to the above methods, the resulting pure cotton stained denim was determined to have Grade 4-5 dry rubbing fastness, Grade 4-5 wet rubbing fastness and Grade 5 light fastness, and the fixation degree of the dye ink was 95%. Example 3: Transfer dyeing of stretch cotton denim fabric In Example 3, the same steps as in Example 1 were used to transfer dye stretch cotton denim fabric. The differences were as follows: Stretch cotton denim fabric: Size: 7X16/70 D; Width: 50-52 inches; Weight: 11.5 OZ; Composition: 97% cotton and 3% stretch spandex. A stripping enzyme broth used contained 0.8% α-amylase, 0.9% NaCl, 0.3% sorbitan fatty acid ester, and deionized water balance (up to 100%). A dyeing accelerator liquid used contained 5% a dyeing accelerator, 2% synthetic tragacanth gum, 3% polysiloxane ether, 3% higher fatty alcohol sodium sulfate, and a balance of deionized water (up to 100%). The staining promoter is represented as the formula below and its nuclear magnetic resonance spectrum and infrared spectrum are shown in FIG. 5a and 5b. NaoýîýOýCHz- GHz-î N_`/| 7-& where 1 part p-phenylhydroxymethyl trimethylammonium hydrochloride (purchased from Sigma-Aldrich, analytically pure) was added dropwise into each of the two reactors. After completion of the dropwise addition, the reaction was continued for 30-60 minutes. The NaCl produced in the reaction was filtered and the pH of the solution was adjusted to 6.5-7 with hydrochloric acid, thus obtaining 2 aliquots of the same epoxy derivatives. Then, under room temperature and stirring conditions, a 32% excess of concentrated ammonia water was added dropwise into each of the reactors containing the epoxy derivatives. After completion of the dropwise addition, the reaction continued for 3-4 hours. Excess ammonia was then removed under vacuum at 80°C and two aliquots of the same amino derivatives of p-phenylhydroxymethyl trimethylammonium hydrochloride were taken. Then, in a homogeneous mixing environment at 0-5°C, a 1:1 molar ratio of 1,3,5-monochloro-s-triazine and p-(ß-sulphatoethylsulfonyl)aniline solution in acetone was slowly added to an aliquot of the amino derivatives obtained above. was added slowly drop by drop. The pH of the reaction was adjusted and controlled to 6.5 with a Na 2 CO 3 aqueous solution as necessary until the reaction was completed and a preliminary product was obtained. Meanwhile, the addition of the Na2CO3 aqueous solution was stopped and the pH of the solution remained at 6.5. The reaction system containing the precursor was heated to 35-40°C and another aliquot of the resulting amino derivatives was added dropwise with stirring. The pH of the reaction was also adjusted and controlled to 6.5 with a Na 2 CO 3 aqueous solution until the reaction was completed, yielding a staining promoter. Meanwhile, the addition of the Na2003 aqueous solution was stopped and the pH of the solution remained at 6.5. The anilox rollers (2) used in step 2 were ceramic anilox rollers (2) with a line count of 60 lines/cm. The formulation of the reactive dye ink used is as follows: Composition % weight Slurry paste 65% Reactive dyes 5% Rare earth drier (rare earth naphthenates, fineness 55% 05 micron) Resistance S 1% Dispersant (phenol aldehyde condensate sulfonate dispersant) 3% Surface tension regulator (Efka 3570N from BASF) 0.5% Purified water Make up to 100% The reactive dyes were Sumifix Supra reactive dyes (Sumifix Supra Navy Blue 2GF) from SUMlTOMO (Japan). The plate rollers used in Step 3 were rotary screens. A material of the surface of the distribution blanket belt was a layer of rubber coating with a thickness of 6 mm. The rubber is chlorosulfonated polyethylene rubber with a surface hardness of 55°Sh. The fixing used was baking fixing. According to the above methods, it was determined that the obtained stretch cotton stained denim had a dry friction fastness of Grade 4-5, a wet friction fastness of Grade 3.5-4 and a light fastness of Grade 4, and the fixation degree of the dye ink was 88%. Example 4: Transfer dyeing of stretch cotton denim fabric In Example 4, the same steps as in Example 3 were used to transfer stretch cotton denim fabric, except that two jobs containing ror were replaced with reactive dyes of Sumifix Supra reactive dyes from SUMlTOMO (Japan). Two fluorine-containing reactive dyes were synthesized as described in Example 2. Cibacron F reactive dyes from Huntsman were replaced with Liyuansu FL dyes from Color Root (Liyuansu Blue FL-RN). The infrared spectrum of a dried sample of the reactive dyes of the two prepared roro-containing jobs is shown in FIGURE 6. According to the above methods, it was determined that the obtained stretch cotton denim had a fastness to dry friction of Grade 4-5, a fastness to wet friction of Grade 4-4.5 and a light fastness of Grade 4, and the fixation degree of the dye ink was 95%. Technical solutions of the above embodiments are preferred embodiments of the present invention, various improvements and variations can be made without departing from the principles of the present invention, and these improvements and variations will fall within the scope of protection of the present invention.TR TR TR