Method for dyeing seaweed fibre materials

Abstract

The present application belongs to the technical field of textile dyeing, and particularly relates to a seaweed fiber material dyeing method. The dyeing method comprises the following steps: (1) performing oil removal treatment on seaweed fiber material, and then placing the seaweed fiber material in a low-melting and low-viscosity solvent for swelling treatment to obtain pretreated seaweed fiber material; (2) immersing the pretreated seaweed fiber material in a modification liquid, performing modification treatment by subsection temperature rising, and washing to obtain modified seaweed fiber material; (3) dyeing the modified seaweed fiber material with a dyeing liquid; (4) dehydrating and drying the dyed seaweed fiber material; and (5) performing post-treatment on the dyed and dried seaweed fiber material to obtain a dyeing finished product. Through improvement of the pretreatment operation process, the dyeing finished product obtained after dyeing of the seaweed fiber material under low-temperature, salt-free and alkali-free dyeing conditions still has excellent dyeing rate and color fastness.

Description

Technical Field

[0001] This invention belongs to the field of textile dyeing technology, and specifically relates to a dyeing method for seaweed fiber materials. Background Technology

[0002] Seaweed fiber has excellent properties such as antibacterial, flame retardant, moisture absorption and biodegradability. However, its molecular chain is rich in carboxyl groups. After ionization in water, the fiber surface carries a strong negative charge, which generates strong electrostatic repulsion with anionic dyes. This results in a dyeing rate that is generally less than 10% and a wash fastness that is mostly below grade 3, which is unqualified.

[0003] While there are some reports on seaweed fiber dyeing technology, many shortcomings remain. Chinese patent CN113186739A discloses a dyeing method for seaweed fiber blended fabrics. This method involves pretreating the seaweed fiber blended fabrics with a five-membered ring quaternary ammonium salt polymer (cationic modification) and then dyeing them with anionic dyes.

[0004] However, this patent has two drawbacks. First, the raw materials and preparation processes for the five-membered ring quaternary ammonium salt polymer are diverse, and the prepared products vary depending on the product, process, and production. The products are unstable and difficult to standardize. Different polymers have different five-membered ring structures, quaternary ammonium salt types, molecular weights, and distributions, all of which directly affect their reactivity and binding mode with fibers, leading to inconsistent modification effects. In other words, from polymers with unclear structures to seaweed fibers with fluctuating performance, and then to extremely sensitive process parameters, even minor changes in any step can be amplified, resulting in inconsistent final product performance. Second, there is the problem of excessively high dyeing temperatures. Seaweed fibers are known to have poor heat resistance; under moist heat treatment at temperatures exceeding 80℃, the fibers are easily damaged. This patent raises the final dyeing temperature to 70-90℃ and performs dyeing treatment for 30-60 minutes. The first washing treatment is at 85-95℃ for 5-15 minutes; drying is performed at 40-80℃, which easily damages the seaweed fibers.

[0005] Chinese patent CN113249986A discloses a seaweed fiber and its dyeing method, which uses the same modified raw materials and principle as CN113186739A; however, it also suffers from the same two drawbacks as CN113186739A: firstly, the modification is unstable, and secondly, the high-temperature treatment causes significant damage to the fiber. The dye bath is heated to 60°C to 90°C (in Example 5, the dye bath temperature reaches as high as 95°C); the color-fixing treatment temperature is 40°C to 80°C; the first washing treatment temperature after color fixation is 85°C to 95°C; all temperatures are above 70°C.

[0006] Chinese patent CN121407407A discloses a dyeing method for improving the dyeing rate and wash durability of seaweed fiber blended fabrics. The dyeing method includes: (1) pretreatment modification: immersing the seaweed fiber blended fabric in an auxiliary agent solution containing a cationic modifier, and then washing it with water; the cationic modifier is N-[(2-hydroxy-3-trimethyl)propyl]chitosan chloride and / or O-acrylamide methyl-N-[(2-hydroxy-3-trimethylammonium)propyl]chitosan chloride; (2) dyeing: immersing the pretreated fabric in a dyeing solution containing reactive dyes for dyeing treatment; (3) color fixing: fixing the dyed fabric in an alkaline color fixing solution; (4) post-treatment: soaping the color-fixed fabric, washing it with water, and finally drying it to complete the dyeing process.

[0007] This patent has two problems. First, during color fixing, the fixing solution concentration is an alkaline solution of 0.04~0.08 g / L; the alkaline agent includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; the liquor ratio for color fixing is 1:2~50, the temperature is 40~80℃, and the time is 10~30 minutes. It is known that seaweed fibers are not resistant to salt and alkali, and the fibers are easily damaged, affecting their mechanical properties. This process is not suitable for dyeing seaweed fibers. Second, the high-temperature treatment causes significant fiber damage: the dyeing temperature is 60~90℃, and the time is 30~60 minutes; the color fixing temperature is 40~80℃, and the time is 10~30 minutes; the soaping temperature is 90~95℃. The high-temperature, strongly alkaline environment causes ion exchange and macromolecular chain breakage in the seaweed fibers, leading to a decrease in the strength of the seaweed fibers, thus affecting the hand feel and mechanical properties of the resulting fabric. Calculations based on the seaweed fiber content before and after dyeing given in Table 1 of this patent show an average decrease of 3.5% in seaweed fiber content, indicating significant damage and loss of seaweed fibers.

[0008] Chinese patent CN115216963A discloses a plasma-based dyeing method for seaweed fibers. This patent pre-treats the seaweed fibers with DMC, then uses plasma technology to perform plasma graft polymerization on the treated seaweed fibers, and finally uses direct dyes for salt-free and alkali-free dyeing. The plasma pre-treatment system treats the seaweed fibers using high-purity nitrogen gas at a flow rate of 800 L / h. The plasma excites the DMC monomer radicals on the seaweed fibers, opening the double bonds of the DMC monomers and providing energy for the polymerization reaction to generate DMC polymers.

[0009] However, there are two problems with this patent. First, the plasma treatment efficiency is insufficient. The effective treatment width of atmospheric pressure jet plasma is usually only a few centimeters to tens of centimeters. When the moving speed is 3m / min, the efficiency of continuous industrial production is low. Second, the consumption of high-purity nitrogen of 800L / h is large, and nitrogen recovery is not considered. Combined with the insufficient plasma treatment efficiency, the two factors together lead to difficulties in industrial transformation.

[0010] Chinese patent CN110318269A discloses a seaweed fiber cationic viscose fabric and its production method that can be dyed without salt or alkali. Through a multi-component fabric design, it utilizes the salt- and alkali-free dyeing properties of cationic viscose fibers to achieve dyeing of seaweed fiber fabric under salt- and alkali-free conditions without damaging the seaweed fibers. However, the dyeing rate of the seaweed fibers and the third component fiber is very low, so the fabric only exhibits a light to medium grayish-brown effect. For example, in Example 2 of this patent, reactive dyeing only dyes the cationic viscose fibers without salt or alkali; the dyeing rate of other fibers is extremely low or non-existent. The specification mentions that the third component fiber is added to improve the fabric's performance and create various special fabric styles. After dyeing, the cationic viscose fibers in the finished fabric are dyed. The pretreatment involves 0-10 wt% hydrogen peroxide at a concentration of 27 wt%, held at 70-100℃ for 10-60 minutes; the dyeing temperature is raised to 60-100℃, the soaping temperature is 40-80℃, and the subsequent washing is done at 40-80℃. However, hydrogen peroxide causes significant damage to seaweed fibers, especially at high temperatures.

[0011] As can be seen from the above, most existing solutions struggle to improve the dyeing depth, dyeing rate, and color fastness of seaweed fibers without damaging them. While single cationic modifiers can improve dyeing performance to some extent in existing technologies, they suffer from the following problems: First, the modifiers only form physical adsorption on the seaweed fiber surface, resulting in weak binding force and poor washability, leading to a significant deterioration of the modification effect during the washing process. Second, in traditional dyeing processes (e.g., "dyeing (salt-induced dyeing) → fixation (alkali-induced dyeing) → soaping → washing → fixing agent fixation → washing → drying"), direct soaping after dyeing causes a large amount of unfixed dye to hydrolyze and fall off, resulting in low dyeing rate and increased wastewater treatment burden. Third, dye migration is severe under high temperature and humidity conditions on seaweed fibers, and conventional drying methods easily cause uneven dyeing defects such as color spots and color differences. Fourth, traditional dyeing processes require the addition of large amounts of sodium sulfate and soda ash, which not only damages the structure of seaweed fibers but also generates high-salt and high-alkali wastewater. Therefore, developing a seaweed fiber modification and dyeing method that can efficiently improve dyeing rate and color fastness while achieving zero-salt and zero-alkali green dyeing has significant industrial value. Summary of the Invention

[0012] The purpose of this invention is to provide a dyeing method for seaweed fiber materials, so that the dyed finished products obtained after dyeing seaweed fiber materials under low temperature, salt-free and alkali-free dyeing conditions can still have excellent dyeing rate and color fastness.

[0013] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The seaweed fiber material dyeing method of the present invention includes the following steps: (1) Pretreatment: The seaweed fiber material is degreased and then placed in a low-melting-point, low-viscosity solvent for swelling treatment to obtain the pretreated seaweed fiber material. (2) Composite cation modification treatment: The pretreated seaweed fiber material is immersed in the modification solution, and the modification treatment is carried out by segmented heating. After washing with water, the modified seaweed fiber material is obtained. (3) Dyeing: The modified seaweed fiber material is dyed with dye solution; (4) Drying after dyeing: Dehydrate and dry the dyed seaweed fiber material; (5) Post-treatment: The dyed and dried seaweed fiber material is post-treated to obtain the dyed finished product.

[0014] in: In step (1), the degreasing treatment involves placing the seaweed fiber material in an aqueous solution containing a degreasing agent and heating it to remove the oil. The concentration of the degreasing agent in the aqueous solution is 0.5~1g / L. The mass ratio of the seaweed fiber material to the aqueous solution containing the degreasing agent is (0.05~0.34):1. The degreasing agent is either TF-101N (a special degreasing agent) or TF-128E (a low-temperature refining degreasing agent).

[0015] The heating rate is 2.5~5℃ / min, the temperature is raised to 65~75℃, and the degreasing treatment time is 8~15min.

[0016] In step (1), the low-melting-point, low-viscosity solvent is prepared by mixing and heating choline chloride, urea, triethanolamine and citric acid; wherein the molar ratio of choline chloride, urea, triethanolamine and citric acid is 1.5:2.75:(0.35~0.6):(0.08~0.15), the heating temperature is 75~85℃, and the heating time is 1~2h; the mass ratio of seaweed fiber material to low-melting-point, low-viscosity solvent is (0.35~0.4):1.

[0017] In step (1), the swelling treatment is performed using ultrasound with a frequency of 20-40 kHz and a treatment time of 30-40 min.

[0018] In step (1), the seaweed fiber material is one of seaweed fiber, seaweed fiber yarn, seaweed fiber knitted fabric or seaweed fiber woven fabric.

[0019] In step (2), the modified solution contains hydroxypropyltrimethylammonium chloride chitosan, glycidyltrimethylammonium chloride and nonionic penetrant. Based on the mass of seaweed fiber material, the amount of hydroxypropyltrimethylammonium chloride chitosan in the modified solution is 2~4% owf, the amount of glycidyltrimethylammonium chloride is 5~6.5% owf, and the concentration of nonionic penetrant is 0.5~1 g / L. The nonionic penetrant is Aikejie KS. The ratio of the amount of seaweed fiber material to the amount of modified solution added in step (1) is (0.047~0.33):1. The seaweed fiber material is in kg and the modified solution is in L.

[0020] In step (2), the segmented heating modification treatment is as follows: the temperature is raised to 57-63℃ at a rate of 1-5℃ / min and held for 20-40 minutes, and then raised to 67-73℃ at a rate of 1-3℃ / min and held for 20-40 minutes; the modified water washing process is as follows: first, water wash at 60±2℃ for 10 minutes, and then water wash at 40±2℃ for 10 minutes.

[0021] In step (3), the reactive dye is the SE series reactive dye of Aihuanda. The dye solution is prepared by adding the dye to water to obtain the dye solution. The amount of dye used is 0.1~5%owf. During dyeing, the temperature is increased to the dyeing temperature at a rate of 2~2.5℃ / min. The dyeing temperature is 38~45℃. The dyeing time is 35~50min. The liquor ratio is 1:(5~20).

[0022] In step (4), a radio frequency dryer or a tenter frame dryer is used for dehydration and drying. When a radio frequency dryer is used, it is a single-stage constant temperature dryer with a drying temperature of 55~64℃. When a tenter frame dryer is used, it is a two-stage gradient drying process, i.e., pre-drying at 55~64℃ and then drying and shaping at 65~75℃.

[0023] In step (5), the post-treatment involves sequentially fixing, soaping, and washing the dyed and dried seaweed fiber material, followed by dehydration and drying; or directly washing and dehydrating the dyed and dried seaweed fiber material. When the total concentration of reactive dye is ≤0.2%owf, the dyed and dried seaweed fiber material is directly washed and dehydrated and dried. When the total concentration of reactive dye is >0.2%owf, the dyed and dried seaweed fiber material is sequentially fixed, soaped, and washed, followed by dehydration and drying. The fixing temperature is 50~60℃, and the fixing time is 15~25min. The washing temperature after fixing is 57~65℃, and the washing time is 10min. The bath ratio for fixing, soaping, and washing is the same, which is 1:(5~20). The dehydration and drying process is the same as in step (4).

[0024] The improvement of the dyeing process in this invention: (I) One-bath two-step composite modification pretreatment process This invention targets seaweed fiber materials, using hydroxypropyltrimethylammonium chloride chitosan and glycidyltrimethylammonium chloride as composite modifiers, and completing the pretreatment in two steps with a temperature gradient in the same treatment bath: Step 1 (Uniform Cation Enrichment): First, utilizing the macromolecular structure and high cation density of hydroxypropyltrimethylammonium chloride chitosan, electrostatic adsorption and deposition are achieved throughout the interior and surface of seaweed fibers, forming a uniform and high-density cation-enriched layer inside and outside the fiber. Step 2 (Covalent Cross-linking Anchoring): The small-molecule epoxy compound glycidyltrimethylammonium chloride can penetrate into the inner layer of the fiber and undergo a covalent cross-linking reaction with the active groups such as hydroxyl groups on the seaweed fiber molecular chains and the physically adsorbed hydroxypropyltrimethylammonium chloride chitosan molecules, permanently locking the physically adsorbed layer through chemical bonds. Through the synergistic effect of these two steps, an ordered gradient stable structure is finally constructed inside the fiber, consisting of an outer high-density cation adsorption layer and an inner covalently cross-linked stable layer.

[0025] (II) Low-temperature dyeing process Reactive dyeing typically involves temperatures above 60°C. This invention, based on composite modification treatment, utilizes the SE series reactive dyes from Aihuanda to achieve a breakthrough in low-temperature dyeing and low-temperature soaping.

[0026] (III) Innovation and Adjustment of Dyeing Process Optionally, the present invention can adjust the traditional dyeing process flow, changing the conventional dyeing → soaping → color fixing → drying process to dyeing → drying → color fixing → soaping and water washing → drying.

[0027] In this process, after the dyeing process is completed and before the color-fixing process, a drying treatment is carried out first. This allows the dye molecules to fully penetrate into the fiber as the water evaporates, and increases the binding force between the dye and the fiber. This avoids the waste of a large amount of unfixed dye due to hydrolysis caused by direct soaping after dyeing in traditional processes, and effectively improves the dye utilization rate.

[0028] First fix the color and then soap wash. This process firmly fixes the dye onto the fiber before soap washing and water washing. This makes it less likely for the color to fade when the consumer washes the product. First, it effectively increases the dye uptake rate, and second, it significantly improves color fastness.

[0029] (iv) Two-stage gradient drying and color-locking process Optionally, considering the high swelling properties of pure seaweed fibers and the tendency of dyes to migrate at high temperatures, a two-stage gradient heating and drying process can be adopted. The first stage is low-temperature pre-drying: pre-drying is carried out at 55~64℃ to slowly evaporate free moisture on the fiber surface, allowing dye molecules to initially locate themselves and preventing rapid migration of dyes to the fiber surface due to rapid water evaporation. The second stage is low-temperature drying: drying is carried out at 65~75℃, ensuring that the fiber quality is not damaged by high temperatures while firmly locking in the dye molecules that have penetrated into the fiber, thus improving dyeing uniformity.

[0030] (v) Dyeing performance and scope of application After the above-mentioned composite modification treatment, the seaweed fiber can be dyed with reactive dyes in a salt-free and alkali-free green throughout the entire process, avoiding the degradation and damage to the seaweed fiber caused by the traditional high-salt and high-alkali dyeing process.

[0031] The beneficial effects of this invention are as follows: (1) Pretreatment stage: Choline chloride (ChCl, decomposes at about 302℃) and urea (melting point 133℃) are both high-melting-point solids in their pure state. Their crystals form regular ionic or hydrogen bond networks with high lattice energy, preventing them from penetrating fibers in liquid form at room temperature. When the two are mixed in a molar ratio of 1.5:2.75 and further compounded with triethanolamine (TEOA) and citric acid, and then heated, the ChCl dissociates into Cl... - As a strong hydrogen bond acceptor, it forms multiple hydrogen bonds with the NH of urea, the OH of TEOA, and the OH of citric acid, which destroys the original crystal structures of ChCl and urea and reconstructs them into a three-dimensional hydrogen bond network. The lattice energy of the system is greatly reduced, which is the source of the "low melting point" characteristic.

[0032] In the classic ChCl-urea eutectic solvent, the molar ratio of the two is usually 1:2, in which case both urea and NH₄⁺ react with Cl₂. - With sufficient coordination, the hydrogen bond network is relatively rigid and the viscosity is relatively high. This invention uses a ChCl-rich ratio of 1.5:2.75, resulting in the presence of some free Cl- that is not fully coordinated with urea in the system. - This increases the mobility and active sites of the hydrogen bond network, and reserves interaction sites for subsequent competitive hydrogen bonding with hydroxyl / carboxyl groups on the fiber chain. Based on this, the compounded TEOA, with its multi-site, sterically hindered structure composed of trihydroxyl groups and tertiary amine nitrogen, inserts into the gaps in the ChCl-urea hydrogen bond network: its hydroxyl groups and Cl... - Urea forms moderately strong hydrogen bonds that can undergo reversible "break-and-bond" reactions, providing structural buffering for the rigid network (similar to intramolecular plasticization), thereby significantly reducing the system viscosity—the key source of its "low viscosity" characteristic. Citric acid participates in the construction of the three-dimensional hydrogen bond network, providing additional connection points and making the three-dimensional hydrogen bond network more stable. This is conducive to the formation of steady-state low-melting-point properties and is the core functional component for subsequent controllable decalcification of seaweed fibers. The four components work synergistically to construct a solvent system that combines low melting point and low viscosity (high fluidity), creating the prerequisites for its penetration into the fiber interior.

[0033] The main component of seaweed fiber is calcium alginate, whose molecular chain is rich in -COO. - and -OH:G block through Ca 2+ Multi-point coordination forms a dense "egg-box" crystalline region, while the amorphous region depends on interchain -COOH... - OOC-、-OH···- OOC-hydrogen bonds and some Ca 2+ Cross-linking forms a tight network, making it difficult for conventional dyes and modifiers to diffuse into it. The low-melting-point, low-viscosity solvent of this invention, with its high fluidity due to its low viscosity, can effectively overcome the interfacial tension on the fiber surface. Under the synergistic effect of the microjets and shock waves generated by ultrasonic cavitation, it disrupts the stagnant boundary layer on the fiber surface, accelerating the mass transfer penetration of the solvent into the amorphous region. The microscopic instantaneous high temperature and pressure generated when the ultrasonic cavitation bubbles collapse can also locally activate chain segments and weaken inter-chain interactions, while the macroscopic system temperature remains mild, preventing thermal damage to the fiber. After penetrating the amorphous region, the three-dimensional hydrogen bond network achieves controllable fiber swelling through two parallel and synergistic pathways: one is competitive substitution of hydrogen bonds, where free Cl- in the solvent... - As a strong hydrogen bond acceptor, it forms hydrogen bonds with -OH and -COOH on the algal fiber chain, while the NH in urea acts as a hydrogen bond donor, forming hydrogen bonds with -COO on the fiber chain. - The first method involves the formation of hydrogen bonds, which competitively replace the original interchain hydrogen bonds in the fiber, increasing the interchain distance, loosening the chain segments, and increasing the free volume. The second method involves coordinated competitive and controllable decalcification, where the three carboxyl groups of citric acid can react with Ca... 2+ The formation of chelates (calcium citrate complexes) with moderate stability constants allows TEOA hydroxyl groups to also assist in coordination. The two complexes competitively coordinate from the amorphous region to unsaturated, highly exposed CaO. 2+ Partial Ca is removed at the crosslinking point 2+ , making Ca 2+ Local relaxation of the cross-linked network. The above-mentioned decalcification process was strictly limited to the amorphous region and the fiber surface, while the egg-box structure in the crystalline region remained intact. This is because: ① the amounts of citric acid and TEOA in the system were relatively small, resulting in limited depth of action; ② the Ca in the crystalline region... 2+ The fiber is tightly wrapped by multiple oxygen atoms in two G blocks, resulting in saturated coordination and significant steric hindrance, making it difficult for solvent molecules to penetrate. Furthermore, the swelling treatment time is limited (30-40 min), and diffusion and coordination exchange have not yet reached the crystalline region. Therefore, the fiber will neither dissolve due to excessive decalcification nor experience a collapse in strength.

[0034] The aforementioned swelling is essentially a non-hydrolyzed, non-oxidative physical-coordination swelling: the entire process does not involve the hydrolysis of glycosidic bonds catalyzed by strong bases / acids, nor does it involve the oxidative breakage of molecular chains caused by oxidants. Therefore, the main chain of seaweed fiber remains intact and the fiber cross-section is smooth. The direct result of the swelling is that the diffusion channels of the amorphous region are precisely opened, which creates the necessary spatial conditions for the penetration and diffusion of glycidyltrimethylammonium chloride small molecules into the inner layer of the fiber in the subsequent step (2) and for the enrichment and deposition of hydroxypropyltrimethylammonium chloride chitosan inside and outside the fiber. It also significantly reduces the activation energy for the subsequent internal diffusion of reactive dye molecules.

[0035] In summary, the three-dimensional hydrogen bond network constructed from choline chloride, urea, triethanolamine, and citric acid, through a multi-synergistic mechanism of "low melting and low viscosity promoting penetration - hydrogen bond competition loosening the chain - coordination competition controllable decalcification - ultrasonic mass transfer enhancement," precisely and controllably opens amorphous region channels without damaging the seaweed fiber backbone and crystalline region, laying a crucial structural foundation for subsequent composite cationic modification and low-temperature staining.

[0036] (2) By using choline chloride, urea, triethanolamine and citric acid to prepare a low-melting-point, low-viscosity solvent in the pretreatment stage to swell the seaweed fiber, the triethanolamine has reversibility in the three-dimensional hydrogen bond network, which makes it easier for triethanolamine to form an organic weak base layer in the amorphous region of the seaweed fiber. The small molecular size of glycidyltrimethylammonium chloride can diffuse into the amorphous region through the channels opened by the three-dimensional hydrogen bond network. The terminal epoxy group of glycidyltrimethylammonium chloride is easier to open the ring and graft in the organic weak base layer environment, thereby covalently introducing quaternary ammonium cations into the fiber. After covalent cross-linking, it is resistant to washing and does not migrate, which fundamentally solves the defect of "single modifier only physically adsorbs and deteriorates after washing" in the background technology. The high dosage of glycidyltrimethylammonium chloride ensures the density of cationic sites inside the seaweed fiber; the small molecule epoxy compound of glycidyltrimethylammonium chloride can penetrate into the inner layer of the fiber and undergo covalent cross-linking reaction with active groups such as hydroxyl groups on the seaweed fiber molecular chain and physically adsorbed hydroxypropyltrimethylammonium chloride chitosan molecules, locking the physically adsorbed layer through chemical bonds; the covalent grafting of glycidyltrimethylammonium chloride provides the chemical basis for the anti-peeling of the hydroxypropyltrimethylammonium chloride chitosan adsorption layer.

[0037] This invention significantly improves the durability of the modified pretreatment effect: It overcomes the inherent shortcomings of single-agent modification by innovatively adopting a dual-cationic composite modification technology of hydroxypropyltrimethylammonium chloride chitosan and glycidyltrimethylammonium chloride. Through the composite modification strategy of "physical adsorption + chemical crosslinking", it not only achieves uniform enrichment of cationic modifier inside and outside the fiber, but also permanently fixes the modified layer through the covalent crosslinking effect of glycidyltrimethylammonium chloride. This effectively solves the problems of traditional single-agent pretreatment effects such as poor water resistance, easy failure, and poor storage stability.

[0038] (3) Traditional process adds sodium sulfate, etc., to use sodium ions to shield the fiber-COO - The electrostatic repulsion between dye anions and seaweed fibers is detrimental to the stability of seaweed fiber strength and also generates a large amount of high-salt wastewater. After the seaweed fiber surface is positively charged by the cationization of epichlorohydrin-trimethylammonium chloride-hydroxypropyltrimethylammonium chloride chitosan composite, the dye anions and the quaternary ammonium salt cations on the fiber surface generate long-range electrostatic attraction, without the need to add additional salts.

[0039] Traditional processes involve adding inorganic alkalis such as sodium carbonate. This is because the active groups on vinyl sulfone dyes (such as vinyl sulfone sulfate in the Aiguanda SE series reactive dyes) are inherently inert. After adding alkali, β-elimination occurs, allowing them to add to the -OH group in the seaweed fiber. Otherwise, the reaction does not occur, and the dye cannot be fixed. In this invention, the -NH2 group on the hydroxypropyltrimethylammonium chloride chitosan is a much stronger nucleophilic site than the -OH group. Under neutral and low-temperature conditions (e.g., 38°C), it can add to the vinyl sulfone group in the Aiguanda SE series reactive dyes to form a bond, thus achieving dye fixation.

[0040] The dense hydrogen bond network and strong calcium ion crosslinking in the amorphous region of seaweed fiber result in weak chain segment movement and small free volume at low temperatures, making it difficult for dye molecules (especially dual-reactive macromolecules) to diffuse into the fiber interior. High temperatures can provide diffusion kinetic energy and accelerate the fixation reaction; however, seaweed fiber has poor heat resistance. Above 70°C, calcium ion loss accelerates, glycosidic bonds hydrolyze, macromolecular chains break, and fiber strength is significantly reduced. The three-dimensional hydrogen bond network of this invention achieves controllable swelling of the amorphous region before dyeing, pre-opening the dye diffusion channels and significantly reducing the diffusion activation energy. The cationization of the glycidyltrimethylammonium chloride-hydroxypropyltrimethylammonium chloride chitosan composite forms electrostatic attraction, providing a strong adsorption driving force for dye molecules and compensating for insufficient kinetic energy of dye molecules at low temperatures. The high reactivity of -NH2 on hydroxypropyltrimethylammonium chloride chitosan allows covalent fixation to occur as early as 38°C. Attached Figure Description

[0041] Figure 1 The image shown is a scanning electron microscope image of the dyed product obtained in Example 1. Figure 2 This is a photograph of the dyed product obtained in Example 2; Figure 3 Scanning electron microscope image of the dyed product prepared in Comparative Example 2; Figure 4 This is a photograph of the dyed product obtained in Example 3; Figure 5 The image shows a scanning electron microscope (SEM) image of the dyed product prepared in Comparative Example 5. Detailed Implementation

[0042] The present invention will now be described and illustrated in detail with reference to the embodiments.

[0043] Example 1 Prepare 46 kg of 40-count seaweed fiber yarn, which needs to be dyed bright blue at a liquor ratio of 1:18. The production process is as follows: (1) Pretreatment: Add seaweed fiber yarn to a 50kg package dyeing machine, add 950L of water at room temperature, add 475g of special degreasing agent TF-101N (provided by Transfar Smart Co., Ltd.), heat to 70℃ at a rate of 2.5℃ / min, treat for 8min and drain to obtain degreased seaweed fiber yarn.

[0044] Choline chloride, urea, triethanolamine, and citric acid were heated at 80°C for 2 hours in a molar ratio of 1.5:2.75:0.6:0.15 to obtain a low-melting-point, low-viscosity solvent. The degreased seaweed fiber yarn was then placed in the low-melting-point, low-viscosity solvent with a mass ratio of seaweed fiber yarn to low-melting-point, low-viscosity solvent of 0.4:1. The mixture was ultrasonically treated at 40 kHz for 30 minutes at room temperature to obtain the pretreated seaweed fiber yarn.

[0045] (2) Composite cationic modification treatment: Prepare a modification solution of 980L, in which the amount of hydroxypropyltrimethylammonium chloride chitosan is 2% owf, the amount of glycidyltrimethylammonium chloride is 6.5% owf, and the concentration of nonionic penetrant Aikejie KS (provided by Shandong Aiwen Biotechnology Co., Ltd.) is 0.5g / L; add the pretreated seaweed fiber yarn to the modification solution, heat it to 60℃ at a rate of 2℃ / min, keep it at 60℃ for 30min, and then heat it to 70℃ at a rate of 1℃ / min and keep it at 70℃ for 30min. After modification treatment, wash it twice with water. First, wash it with water at 58℃ for 10min, drain the water, and then wash it with water at 40℃ for 10min. The water volume for both washes is 830L, and the modified seaweed fiber yarn is obtained.

[0046] (3) Dyeing: Avenda SE series reactive dyes (provided by Angga Chemical (China) Co., Ltd.) were used, with BlueSE amounting to 2.183% owf and Red SE amounting to 0.016% owf. Blue SE and Red SE were added to water at room temperature to obtain 830L of dye liquor. Modified seaweed fiber yarn was added, and the temperature was raised to the dyeing temperature of 38℃ at a rate of 2℃ / min and held for 50min.

[0047] (4) Drying after dyeing: centrifugal dehydrator is used for dehydration, and dual-zone radio frequency dryer is used for drying. The conveyor speed of the dryer is 8 meters / hour, and the drying temperature is 64℃.

[0048] (5) Fixing: Brilliant Fast FIX fixing agent (provided by Angco Chemical (China) Co., Ltd.) was used. The dosage of Brilliant Fast FIX fixing agent was 4.398% owf. 830L of fixing solution was prepared and the color was fixed at 55℃ for 20min. After fixing, the product was washed with water at 60℃ for 10min.

[0049] (6) Soap washing: Weigh 1660g of Aikejie JH (provided by Shandong Aiwen Biotechnology Co., Ltd.), prepare soap washing solution with a concentration of 2g / L, soap wash at 60℃ for 10min and drain. Weigh 1245g of Aikejie JH, prepare soap washing solution with a concentration of 1.5g / L, soap wash at 60℃ for 10min and drain.

[0050] (7) Wash with water after soaping: wash with water at 60℃ for 10 minutes, then wash with water at 40℃ for 10 minutes. The water volume for both washes is 830L.

[0051] (8) Dehydrate and dry to obtain the dyed finished product. The scanning electron microscope image of the dyed finished product is shown in the figure. Figure 1 The specific operation process of dehydration and drying is the same as step (4). The specific operation process and parameters of post-dyeing drying are as follows.

[0052] Comparative Example 1 The composite cation modification treatment in step (2) is not performed, and the remaining operation steps are the same as in Example 1.

[0053] Example 2 Prepare 28kg of 40-count seaweed fiber knitted fabric, which needs to be dyed dark red at a liquor ratio of 1:10. The production process is as follows: (1) Pretreatment: Add the seaweed fiber knitted fabric to a 30kg O-type overflow dyeing machine, add 83L of water at room temperature, add 83g of special degreasing agent TF-101N (provided by Transfar Smart Co., Ltd.) to obtain an aqueous solution, heat it to 65℃ at a rate of 5℃ / min, treat for 12min and drain the water to obtain the degreased seaweed fiber knitted fabric.

[0054] Choline chloride, urea, triethanolamine, and citric acid were heated at 75°C for 2 hours in a molar ratio of 1.5:2.75:0.5:0.1 to obtain a low-melting-point, low-viscosity solvent. The degreased seaweed fiber knitted fabric was then placed in the low-melting-point, low-viscosity solvent with a mass ratio of seaweed fiber knitted fabric to low-melting-point, low-viscosity solvent of 0.4:1. The fabric was then ultrasonically treated at 20kHz for 40 minutes at room temperature to obtain the pretreated seaweed fiber knitted fabric.

[0055] (2) Composite cationic modification treatment: Prepare 85L of modification solution, in which the amount of hydroxypropyltrimethylammonium chloride chitosan is 4% owf, the amount of glycidyltrimethylammonium chloride is 5% owf, and the concentration of nonionic penetrant Aikejie KS (provided by Shandong Aiwen Biotechnology Co., Ltd.) is 0.7g / L; add the pretreated seaweed fiber knitted fabric to the modification solution, heat to 63℃ at a rate of 2℃ / min, keep warm for 25min, then heat to 73℃ at a rate of 1℃ / min, and keep warm for 25min. After modification treatment, wash twice with water. First wash with water at 62℃ for 10min, drain and then wash with water at 38℃ for 10min. The water volume for both washes is 280L. After washing, dehydrate, open the fabric, and dry with a hot air tenter for later use to obtain the modified seaweed fiber knitted fabric.

[0056] (3) Dyeing: Avenda SE series reactive dyes (provided by Angga Chemical (China) Co., Ltd.) were used, with Red SE amounting to 5.0% owf; Red SE was added to water at room temperature to obtain 280L of dye liquor, and the modified seaweed fiber knitted fabric was added. The temperature was raised to 40℃ at a rate of 2℃ / min and held for 40min.

[0057] (4) Drying after dyeing: centrifugal dehydrator is used for dehydration, opening machine and stretching dryer are used for drying and shaping. The conveyor speed of the dryer is 25m / min. A two-stage gradient drying and color-locking process is adopted, namely, low temperature pre-drying at 64℃ and drying and shaping at 75℃.

[0058] (5) Fixing: Brilliant Fast FIX fixing agent (provided by Angco Chemical (China) Co., Ltd.) was used. The amount of Brilliant Fast FIX fixing agent was 10% owf. 280L of fixing solution was prepared and the color was fixed at 50℃ for 25min. After fixing, the product was washed with water at 65℃ for 10min.

[0059] (6) Soap washing: Weigh 560g of soap washing agent C-305 (provided by Nichih Chemical (China) Co., Ltd.), prepare soap washing solution, wherein the concentration of soap washing agent C-305 is 2g / L, soap wash at 60℃ for 10min and drain. Weigh 420g of soap washing agent C-305, prepare soap washing solution, wherein the concentration of soap washing agent C-305 is 1.5g / L, soap wash at 60℃ for 10min and drain.

[0060] (7) Wash with water after soaping: wash with water at 60℃ for 10 minutes, then wash with water at 40℃ for 10 minutes. The water volume for both washes is 280L.

[0061] (8) Dehydrate and dry to obtain the dyed finished product. The specific operation process is the same as that in step (4) post-dyeing drying. See the actual picture of the dyed finished product. Figure 2 .

[0062] Comparative Example 2 The composite cation modification treatment in step (2) is not performed. In step (3) for staining: staining is performed at room temperature, then the temperature is increased to 60°C at a rate of 2°C / min, and the staining is maintained at this temperature for 10 minutes. Then, 40 g / L of sodium sulfate is added, and staining continues at 60°C for 20 minutes. Next, 20 g / L of sodium carbonate is added, and staining continues at 60°C for 25 minutes. Finally, the staining solution is drained. The remaining steps are the same as in Example 2. The scanning electron microscope image of the obtained dyed product is shown below. Figure 3 .

[0063] Example 3 Prepare 7.4 kg of 32-count seaweed fiber woven fabric. This fabric, after desizing, has a width of 149 cm and needs to be dyed dark yellow with a liquor ratio of 1:5. The production process is as follows: (1) Pretreatment: The seaweed fiber woven fabric is added to the dyeing machine. The low-temperature refining degreasing agent TF-128E (provided by Transfar Smart Logistics Co., Ltd.) is used to prepare 37L of 0.5g / L aqueous solution. The water solution is added, the dyeing machine speed is set to 90m / min, and the treatment is carried out at 70℃ for 9min to obtain the degreased seaweed fiber woven fabric.

[0064] Choline chloride, urea, triethanolamine, and citric acid were heated at 80°C for 1.5 hours in a molar ratio of 1.5:2.75:0.35:0.08 to obtain a low-melting-point, low-viscosity solvent. The degreased seaweed fiber woven fabric was then placed in the low-melting-point, low-viscosity solvent with a mass ratio of seaweed fiber woven fabric to low-melting-point, low-viscosity solvent of 0.35:1. The fabric was ultrasonically treated at 30 kHz for 35 minutes at room temperature to obtain the pretreated seaweed fiber woven fabric.

[0065] (2) Composite cationic modification treatment: Prepare 72L of modification solution, in which the amount of hydroxypropyltrimethylammonium chloride chitosan is 3% owf, the amount of glycidyltrimethylammonium chloride is 6% owf, and the concentration of nonionic penetrant Aikejie KS (provided by Shandong Aiwen Biotechnology Co., Ltd.) is 1g / L; add the pretreated seaweed fiber woven fabric to the modification solution, set the speed of the dyeing machine to 75m / min, raise the temperature to 60℃ at a rate of 5℃ / min, treat for 40min, then raise the temperature to 70℃ at a rate of 3℃ / min, treat for 40min, and drain the solution. After modification treatment, wash twice with water. First wash with water at 60℃ for 10min, drain the solution, and then wash with water at 40℃ for 10min to obtain the modified seaweed fiber woven fabric.

[0066] (3) Dyeing: Aqva SE series reactive dyes (provided by Angga Chemical (China) Co., Ltd.) were used, with Yellow SE amounting to 4.0% owf. Yellow SE was added to water at room temperature to obtain 120L of dye liquor. It was added to the modified seaweed fiber woven fabric, and the speed of the dyeing machine was set to 90m / min, the dyeing temperature was 42℃, and 10 dyeing passes were performed.

[0067] (4) Drying after dyeing: centrifugal dehydrator is used for dehydration, and opening machine and stretching dryer are used for drying and shaping. The conveyor speed of the dryer is 25m / min. A two-stage gradient drying and color-locking process is adopted, namely, low temperature pre-drying at 55℃ and drying and shaping at 65℃.

[0068] (5) Fixing: Brilliant Fast FIX fixing agent (provided by Angco Chemical (China) Co., Ltd.) was used. The amount of Brilliant Fast FIX fixing agent was 8% owf. The fixing solution was prepared and the color was fixed at 60℃ for 20 min. After fixing, the color was washed with water at 63℃ for 10 min.

[0069] (6) Soap washing: Weigh 300g of Aikejie JH (provided by Shandong Aiwen Biotechnology Co., Ltd.), prepare soap washing solution, wherein the concentration of Aikejie JH is 2g / L, and soap wash at 70℃ for 30min.

[0070] (7) Wash with water after soaping: wash with water at 60℃ for 15 minutes, then wash with water at 40℃ for 10 minutes.

[0071] (8) Dehydration and drying to obtain the dyed finished product. Specific operation steps (4) Post-dyeing drying: specific operation process and parameters. See the actual picture of the dyed finished product. Figure 4 .

[0072] Comparative Example 3 In step (2), glycidyltrimethylammonium chloride is not added to the modified solution; only hydroxypropyltrimethylammonium chloride chitosan is added. The remaining operation steps are the same as in Example 3.

[0073] Comparative Example 4 In step (2), hydroxypropyltrimethylammonium chloride chitosan is not added to the modified solution; only glycidyltrimethylammonium chloride is added. The remaining operation steps are the same as in Example 3.

[0074] Example 4 Prepare 4g of seaweed fiber, which needs to be dyed light yellow-brown at a liquor ratio of 1:20. The production process is as follows: (1) Pretreatment: The seaweed fiber was added to the small sample dyeing machine and a 0.8 g / L aqueous solution of TF-128E (provided by Transfar Smart Co., Ltd.) was prepared using a low-temperature refining degreasing agent. The aqueous solution was added and heated to 75°C at a rate of 3.5°C / min. After treatment for 15 min, the water was drained to obtain the degreased seaweed fiber.

[0075] Choline chloride, urea, triethanolamine, and citric acid were heated at 85°C for 1 hour in a molar ratio of 1.5:2.75:0.6:0.08 to obtain a low-melting-point, low-viscosity solvent. The degreased seaweed fiber was then placed in the low-melting-point, low-viscosity solvent with a mass ratio of seaweed fiber to low-melting-point, low-viscosity solvent of 0.38:1. The mixture was ultrasonically treated at 40 kHz for 36 minutes at room temperature to obtain the pretreated seaweed fiber.

[0076] (2) Composite cationic modification treatment: Prepare 85 mL of modification solution, in which the amount of hydroxypropyltrimethylammonium chloride chitosan is 2.5% owf, the amount of glycidyltrimethylammonium chloride is 6.5% owf, and the concentration of nonionic penetrant Aikejie KS (provided by Shandong Aiwen Biotechnology Co., Ltd.) is 0.5 g / L; add the modification solution to the pretreated seaweed fiber, heat to 57℃ at a rate of 1℃ / min, keep at 57℃ for 25 min, then heat to 67℃ at a rate of 2℃ / min, and keep at 67℃ for 25 min. After modification treatment, wash twice with water. First, wash with water at 60℃ for 10 min, drain the water, and then wash with water at 40℃ for 10 min to obtain the modified seaweed fiber.

[0077] (3) Dyeing: Avenda SE series reactive dyes (provided by Angga Chemical (China) Co., Ltd.) were used, with Yellow SE at 0.097% owf, Red SE at 0.008% owf and Blue SE at 0.002% owf. Yellow SE, Red SE and Blue SE were added to water at room temperature to obtain 85 mL of dye solution. Modified seaweed fiber was added, and the temperature was raised to the dyeing temperature of 45℃ at a rate of 2.5℃ / min and held for 35 min.

[0078] (4) Drying after dyeing: After squeezing by hand, simulate production, the fibers gather into a ball and are dried in a dual-zone radio frequency dryer. The conveyor speed of the dryer is 8m / min and the drying temperature is 55℃.

[0079] (5) Washing: Wash at 60℃ for 10 min, then wash at 40℃ for 10 min. The water volume for both washes is 85 mL.

[0080] (6) Dehydrate and dry to obtain the dyed finished product. Specific operation steps (4) Post-dyeing drying specific operation process and parameters.

[0081] Comparative Example 5 High-temperature staining effect: Unlike Example 4, the pretreatment, staining, and washing temperatures are higher, while other conditions are the same. The specific differences are as follows: (1) Pretreatment: Heat to 80℃, treat for 10 min and then drain.

[0082] (2) Composite cation modification treatment: Same as in Example 4.

[0083] (3) Staining: The staining temperature is 60℃ and the staining time is 40min.

[0084] (4) Drying after dyeing: After squeezing by hand, place loosely in the oven and dry with hot air at 90℃ for 1.5 hours.

[0085] (5) Washing: Wash with water at 90°C for 10 minutes, then wash with water at 40°C for 10 minutes.

[0086] Scanning electron microscope image of the dyed product is shown below. Figure 5 .

[0087] Comparative Example 6 In step (1) of the pretreatment process, no choline chloride is added, and the remaining operation steps are the same as in Example 1.

[0088] Comparative Example 7 In step (1) of the pretreatment process, no urea is added, and the remaining operation steps are the same as in Example 1.

[0089] Comparative Example 8 In step (1) of the pretreatment process, triethanolamine is not added, and the remaining operation steps are the same as in Example 1.

[0090] Comparative Example 9 In step (1) of the pretreatment process, citric acid is not added, and the remaining operation steps are the same as in Example 1.

[0091] Implementation effect evaluation

[0092] The performance of the dyed products from the examples and comparative examples was tested, and the specific test results are shown in Tables 1 and 2: Table 1. Performance test results of dyed finished products from Examples 1-4 and Comparative Examples 1-5

[0093] As can be seen from Table 1, Examples 1, 2, 3, and 4 all significantly improved the dyeing rate and color fastness while ensuring that the fibers were not damaged, and have already been industrialized.

[0094] Comparative Example 1, unmodified, has almost no color dyeing effect, failing to meet consumers' demands for color depth and color diversity.

[0095] Comparative Example 2, without modification, with the addition of salt and alkali for dyeing, caused severe damage to the fibers, resulting in a stiff hand feel and making it unusable.

[0096] Comparative Example 3, with hydroxypropyltrimethylammonium chloride chitosan as the sole modifier, exhibited poor color fastness and was prone to fading. The main reason for this was that hydroxypropyltrimethylammonium chloride chitosan had good water solubility and poor binding to fibers.

[0097] Comparative Example 4: The single modification of glycidyltrimethylammonium chloride resulted in a low dyeing rate, which could not meet the color depth requirements. The main reason was that the degree of cationic modification of glycidyltrimethylammonium chloride alone was very low.

[0098] Comparative Example 5: High-temperature dyeing and color-fixing treatments resulted in severe fiber damage and a poor hand feel. High-temperature dyed fibers cannot be spun, dyed yarns are difficult to rewind, and dyed fabrics have poor surface finish, making them unsuitable for industrial applications.

[0099] Table 2. Performance test results of dyed finished products from comparative examples 6-9

[0100] As shown in Table 2, the low-melting-point, low-viscosity solvents in Comparative Examples 5-9 lacked choline chloride, urea, triethanolamine, and citric acid, respectively, resulting in dyeing rates of only 64.87%, 73.14%, 75.56%, and 78.92%, which were lower than the 92.18% of Example 1. The color depth K / S values ​​were all lower than in Example 1, and the fiber cross-sections showed roughness and bifurcation. The wet rubbing fastness was below grade 4, and the light fastness was inferior to Example 1, failing to meet industrialization requirements. This indicates that the four components—choline chloride, urea, triethanolamine, and citric acid—have an irreplaceable synergistic effect in the formation of the low-melting-point, low-viscosity solvent and in the swelling process of seaweed fibers; none can be omitted.

Claims

1. A method for dyeing seaweed fiber materials, characterized in that, Includes the following steps: (1) Pretreatment: The seaweed fiber material is degreased and then placed in a low-melting-point, low-viscosity solvent for swelling treatment to obtain the pretreated seaweed fiber material. (2) Composite cation modification treatment: The pretreated seaweed fiber material is immersed in the modification solution, and the modification treatment is carried out by segmented heating. After washing with water, the modified seaweed fiber material is obtained. (3) Dyeing: The modified seaweed fiber material is dyed with dye solution; (4) Drying after dyeing: Dehydrate and dry the dyed seaweed fiber material; (5) Post-treatment: The dried seaweed fiber material after dyeing is post-treated to obtain the dyed finished product.

2. The dyeing method for seaweed fiber materials according to claim 1, characterized in that, In step (1), the degreasing treatment involves placing the seaweed fiber material in an aqueous solution containing a degreasing agent and heating it to remove the oil. The concentration of the degreasing agent in the aqueous solution is 0.5~1g / L, and the mass ratio of seaweed fiber material to aqueous solution containing degreasing agent is (0.05~0.34):

1.

3. The dyeing method for seaweed fiber materials according to claim 2, characterized in that, The heating rate is 2.5~5℃ / min, the temperature is raised to 65~75℃, and the degreasing treatment time is 8~15min.

4. The dyeing method for seaweed fiber materials according to claim 1, characterized in that, In step (1), the low-melting-point, low-viscosity solvent is prepared by mixing and heating choline chloride, urea, triethanolamine and citric acid; wherein the molar ratio of choline chloride, urea, triethanolamine and citric acid is 1.5:2.75:(0.35~0.6):(0.08~0.15), the heating temperature is 75~85℃, and the heating time is 1~2h; the mass ratio of seaweed fiber material to low-melting-point, low-viscosity solvent is (0.35~0.4):

1.

5. The dyeing method for seaweed fiber materials according to claim 1, characterized in that, In step (1), ultrasonic waves are used during the swelling treatment. The ultrasonic frequency is 20~40kHz and the treatment time is 30~40min.

6. The method for dyeing seaweed fiber materials according to claim 1, characterized in that, In step (1), the seaweed fiber material is one of seaweed fiber, seaweed fiber yarn, seaweed fiber knitted fabric or seaweed fiber woven fabric.

7. The dyeing method for seaweed fiber materials according to claim 1, characterized in that, In step (2), the modified solution contains hydroxypropyltrimethylammonium chloride chitosan, glycidyltrimethylammonium chloride and nonionic penetrant. The amount of hydroxypropyltrimethylammonium chloride chitosan in the modified solution is 2~4%owf, the amount of glycidyltrimethylammonium chloride is 5~6.5%owf, and the concentration of nonionic penetrant is 0.5~1g / L. The ratio of the amount of seaweed fiber material to the amount of modified solution added in step (1) is (0.047~0.33):

1. The seaweed fiber material is in kg and the modified solution is in L.

8. The dyeing method for seaweed fiber materials according to claim 1, characterized in that, In step (2), the segmented heating process is as follows: the temperature is increased to 57~63℃ at a rate of 1~5℃ / min and held for 20~40min, and then increased to 67~73℃ at a rate of 1~3℃ / min and held for 20~40min.

9. The method for dyeing seaweed fiber materials according to claim 1, characterized in that, In step (3), the dye solution is prepared by adding the dye to water to obtain the dye solution. The amount of dye used is 0.1~5%owf. During dyeing, the temperature is increased to the dyeing temperature at a rate of 2~2.5℃ / min. The dyeing temperature is 38~45℃, the dyeing time is 35~50min, and the bath ratio is 1:(5~20).

10. The method for dyeing seaweed fiber materials according to claim 1, characterized in that, In step (5), the post-treatment is to perform color fixing, soaping, water washing and dehydration drying on the seaweed fiber material after dyeing and drying, or to directly wash and dehydrate the seaweed fiber material after dyeing and drying; the color fixing uses a non-ionic color fixing agent, the color fixing temperature is 50~60℃, and the color fixing time is 15~25min.

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