Acidic dyeing and color fixing method for sheep villus fibers

Abstract

The invention relates to the technical field of fiber acid dyeing, and particularly discloses a sheep villus fiber acid dyeing fixation method which comprises the following steps: mixing acetic acid, triethanolamine and cardanol polyoxyethylene (n) ether sulfate to obtain a prefabricated material a; caprolactam is mixed with rhamnolipid, polyvinylpyrrolidone and acylation modified chitosan, and a prefabricated material b is obtained; mesoporous silica, saturated ammonia water, tetraethoxysilane, potassium methoxide, dioxane and succinic anhydride are adopted to prepare a prefabricated material c; adding the prefabricated material a into the prefabricated material b, stirring, then adding the prefabricated material c, uniformly mixing, adjusting the pH value of the system to 5-6, adding cashmere fibers, keeping the temperature at 5-10 DEG C for 10-20 minutes, heating to 40-50 DEG C, keeping the temperature for 10-20 minutes, adding an acid dye and anhydrous sodium sulfate, uniformly stirring, keeping the temperature for 1-2 hours, heating to 80-90 DEG C, keeping the temperature for 30-50 minutes, taking out, washing, and airing at room temperature.

Description

Technical Field

[0001] The invention relates to the technical field of fiber acid dyeing, in particular to a cashmere fiber acid dyeing and color fixing method. Background Art

[0002] The dyeing process is the process of dyeing fiber materials with colors. It relies on the physical or chemical combination of dyes and fibers, or the use of chemical methods to generate dyes on fibers to make the entire textile become a colored object.

[0003] Because of its dense surface and the barrier effect of the hydrophobic scale layer, the dyeing process of wool often needs to be carried out under boiling or near-boiling conditions. Higher dyeing temperatures not only waste energy, but also easily cause severe damage and yellowing of the wool fibers, ultimately affecting the performance of the dyed fabric.

[0004] Acid dyes are a type of dye with an acidic group in its structure, and they are dyed in an acidic medium. Existing acid dyes are widely used for dyeing loose wool / yarn / fabric such as cashmere and wool, but acid dyes are difficult to dye. Some dyes have a high dyeing rate at around 40°C, and the dyeing rate is fast. Especially in the summer when the water temperature in the workshop is high, the starting temperature is often above 40°C, and it is easy to dye unevenly when dyeing light colors, resulting in defects such as color spots.

[0005] The existing acid dyes on the market are mainly weak cationic leveling agents of fatty amine polyethers. Weak cationic leveling agents combine with acid dyes in the early stage of dyeing to solubilize and emulsify acid dyes, thereby achieving the purpose of slow dyeing. However, this reduces the chance of ionic bonding between dyes and fibers to some extent, making it difficult for dye molecules to escape from micelles, resulting in a darker color of the dyeing residual liquid and low utilization of the dye. At the same time, acidic color fixing agents are mostly anionic auxiliaries, which require clean water after dyeing before color fixing. The process is long and water consumption is high, and the pressure of clean production is relatively high.

[0006] How to develop an acid dyeing process for cashmere wool fibers, slow down the interaction between dyes and fibers, reduce the dyeing rate in the initial stage of dyeing, and have good compatibility with acid fixing agents to achieve energy conservation and emission reduction has excellent prospects. Summary of the invention

[0007] The purpose of the present invention is to solve the shortcomings of the prior art and to propose a cashmere fiber acid dyeing and fixing method.

[0008] A cashmere fiber acid dyeing and fixing method comprises the following steps: S1. Add acetic acid and triethanolamine to water and stir evenly, add cardanol polyoxyethylene ether sulfate and stir for 1-2h to obtain a prefabricated material. a ; S2. Add caprolactam into water and stir evenly, add rhamnolipid, polyvinyl pyrrolidone and acylated modified chitosan into water and stir for 1-2h to obtain prefabricated material. b ; S3, adding mesoporous silica to ethanol aqueous solution and stirring evenly, adding saturated ammonia water thereto and stirring for 10-20 minutes, adding tetraethyl orthosilicate thereto dropwise while stirring, ultrasonically treating after complete addition, centrifuging, washing, drying, adding to tetrahydrofuran, adding potassium methoxide and stirring for 1-2 hours, adding dioxane, adjusting the system temperature to 80-90°C, adding glycidol and stirring for 1-2 hours, adding succinic anhydride, stirring for 2-4 hours under nitrogen protection, adding ethanol and stirring for 1-2 hours, centrifuging, washing, and vacuum drying to obtain a preform c ; S4, prefabricated material a Add to preform b Stir for 10-30 minutes, then add the prefabricated material c Mix evenly, adjust the pH value of the system to 5-6, add cashmere fiber, keep warm at 5-10℃ for 10-20min, increase the temperature to 40-50℃, keep warm for 10-20min, add acid dye and anhydrous sodium sulfate, stir evenly, keep warm for 1-2h, increase the temperature to 80-90℃, keep warm for 30-50min, take out, wash with water, and dry at room temperature.

[0009] Preferably, in S1, cardanol polyoxyethylene ether sulfate is obtained by reacting cardanol polyoxyethylene ether with aminosulfonic acid using urea as a catalyst.

[0010] Preferably, in S1, the mass ratio of acetic acid, triethanolamine and cardanol polyoxyethylene ether sulfate is 1-3:1-3:20-40.

[0011] Preferably, in S2, the mass ratio of caprolactam, rhamnolipid, polyvinyl pyrrolidone and acylated modified chitosan is 5-10:5-15:1-2:1-2.

[0012] Preferably, in S2, the acylated chitosan is citric acid acylated chitosan, which is obtained by using citric acid and chitosan as raw materials and sodium hypophosphite as a catalyst. See reference [1].

[0013] [1] Cui Wenhui. Study on the structure and functional properties of chitosan modified by citric acid acylation and its products[D]. Chinese Academy of Agricultural Sciences[2024-10-09].DOI:CNKI:CDMD:2.1016.174787. Preferably, in S3, the particle size of the mesoporous silica is 50-200 nm.

[0014] Preferably, in S3, the mass ratio of mesoporous silica, saturated ammonia water, tetraethyl orthosilicate, potassium methoxide, dioxane, glycidol and succinic anhydride is 5-10: 1-3: 1-5: 0.01-0.1: 5-10: 1-2: 0.01-0.1.

[0015] Preferably, in S3, the mass fraction of the ethanol aqueous solution is 60-70%.

[0016] Preferably, in S4, the prefabricated material a , Prefabricated materials b , Prefabricated materials c The mass ratio of acid dye and anhydrous sodium sulfate is 70-110:50-90:1-2:5-10:1-2.

[0017] Preferably, in S4, after the cashmere wool fibers are added, the bath ratio of the system is 1:50.

[0018] Preferably, in S4, a sulfuric acid aqueous solution with a mass fraction of 5-8% is used to adjust the pH value of the system to 5-6.

[0019] Preferably, in S4, the acid dye is MG-R1.

[0020] Beneficial effects: The present invention adopts chemical modification and surfactant compounding technology to dye and solidify cashmere wool fibers, wherein aminosulfonic acid is used to anionize bio-based cardanol polyoxyethylene ether, and the cardanol polyoxyethylene ether is modified by adjusting the n Mix with aminosulfonic acid to make the prefabricated material a It not only has the excellent performance of polyoxyethylene chain type and sulfonate type anionic surfactants, but also can improve the compatibility with the cationic amino groups on cashmere fibers and improve the regulation of the positive charge on the fiber surface while meeting environmental protection requirements.

[0021] Acid dyes (especially MG-R1) can be compounded with polyvinyl pyrrolidone and acylated modified chitosan. The oxygen-rich and nitrogen-rich structure of polyvinyl pyrrolidone can chelate metal ions in water, which can significantly improve the leveling effect. Acylated modified chitosan has good affinity with cashmere fibers and can effectively reduce the surface potential, thereby giving the dye molecules good and stable slow dyeing properties.

[0022] The present invention deposits nano-silica on mesoporous silica, grafts a hyperbranched structure, and then performs carboxyl functionalization, which is not only more conducive to the entry of acid dyes, but also realizes efficient loading of dyes due to its high specific surface area and pore volume. The steric hindrance effect of the hyperbranched structure and the terminal carboxyl functional group have high stability. a , Prefabricated materials b Prepare dyeing auxiliary agent, and then prepare the prefabricated material cAdd to dyeing auxiliaries, then add cashmere wool fibers to it, pre-made c The active carboxyl group at the end can be combined with the surface of the cashmere fiber structure, thereby increasing the binding degree of acid dyes to cashmere fibers, thereby increasing the dye uptake rate and improving the fastness of the dye. At the same time, the fiber strength is high and the mechanical properties are less lost.

[0023] At the same time, prefabricated c First, it is combined with cashmere fibers, and then acid dyes are added. At low temperatures, it can effectively delay the rapid dyeing of acid dyes. As the temperature rises, the acid dyes are evenly adsorbed, effectively preventing the dyes from quickly dyeing the fibers. The combined effect of triethanolamine and caprolactam can better dissolve the acid dyes and further enhance the uniformity of dye coloring on the fibers.

[0024] The invention does not contain alkylphenol polyoxyethylene ether compounds and phosphate structures, is biodegradable, and is more friendly to the ecological environment. At the same time, it has high efficiency and stable level dyeing performance when dyeing with acid dyes, is more suitable for high-end fabric products, and has broad market prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a photograph of a woven fabric of cashmere wool fibers after dyeing and fixing obtained by the method of Example 5.

[0026] Figure 2 This is a comparison chart of the desizing rate and K / S value of cashmere wool fibers after dyeing and fixation obtained by the methods of Example 5 and Comparative Examples 1-2.

[0027] Figure 3 The figure is a comparison chart of the dye uptake rate and the color fixation rate of the cashmere wool fibers after dyeing and color fixation obtained by the methods of Example 5 and Comparative Examples 1-2.

[0028] Figure 4 This is a comparison chart of the strength retention rates of cashmere wool fibers after dyeing and fixation obtained by the methods of Example 5 and Comparative Examples 1-2.

[0029] Figure 5 This is a comparison chart of the color fastness to dry / wet friction, color fastness to soaping, and color fastness to water of cashmere wool fibers after dyeing and fixing obtained by the methods of Example 5 and Comparative Examples 1-2; wherein the middle level of two adjacent levels in the gray sample card is regarded as half of the sum of the two adjacent levels, such as 4-5 is regarded as 4.5. DETAILED DESCRIPTION

[0030] The present invention will be further explained below in conjunction with specific embodiments.

[0031] Example 1 A cashmere fiber acid dyeing and fixing method comprises the following steps: S1. Stir 40g of cardanol polyoxyethylene ether (CXF-3) and 0.9g of urea evenly, heat to 120°C and continue stirring, add 17g of powdered aminosulfonic acid several times during the stirring process, and the aminosulfonic acid addition process lasts for 3h, then add anhydrous ethanol at a constant temperature of 70°C and stir to promote the dissolution of the product, and vacuum filter; adjust the pH value of the filtrate to 7.5-8.5 with a sodium hydroxide solution with a mass fraction of 30%, then filter, and remove ethanol using a rotary evaporator; dry in a vacuum drying oven at 70°C for 12h to obtain cardanol polyoxyethylene ether sulfate; 10g of acetic acid and 10g of triethanolamine were added to 500g of water and stirred evenly. 200g of cardanol polyoxyethylene ether sulfate was added thereto and stirred at a speed of 1000r / min for 1h to obtain a prefabricated material. a ; S2, add 50g of caprolactam to 400g of water and stir evenly, add 50g of rhamnolipid, 10g of polyvinyl pyrrolidone, and 10g of citric acid acylated modified chitosan thereto, stir at a speed of 1000r / min for 1h, and obtain a prefabricated material. b ; S3. Add 50g of mesoporous silica with an average particle size of 200nm to 300g of 60% ethanol aqueous solution and stir evenly, add 10g of saturated ammonia water and stir for 10min, add 10g of tetraethyl orthosilicate dropwise under stirring, ultrasonically treat for 2h after complete addition, the ultrasonic frequency is 5kHz, centrifuge, wash with deionized water, vacuum dry, add to 200g of tetrahydrofuran, add 0.1g of potassium methoxide and stir for 1h, add 50g of dioxane, adjust the system temperature to 80℃, add 10g of glycidol and stir for 1h, the stirring speed is 1000r / min, add 0.1g of succinic anhydride, stir for 2h under nitrogen protection, add 1000g of ethanol and stir for 1h, centrifuge, wash once with ethanol, vacuum dry, and obtain a prefabricated material. c ; S4, 700g prefabricated material a Add to 500g prefabricated material b Stir at 1000r / min for 10min, then add 10g prefabricated material c Mix evenly, adjust the pH value of the system to 5-6 with a 5% mass fraction of sulfuric acid aqueous solution, add cashmere fiber, the bath ratio is 1:50, keep warm at 5℃ for 10min, increase the temperature to 40℃, keep warm for 10min, add 50g acid dye MG-R1 and 10g anhydrous sodium sulfate, stir evenly, keep warm for 1h, increase the temperature to 80℃, keep warm for 30min, take out, wash with water, and dry at room temperature.

[0032] Example 2 A cashmere fiber acid dyeing and fixing method comprises the following steps: S1. Stir 90g of cardanol polyoxyethylene ether (CXF-14) and 1.65g of urea evenly, heat to 140°C and continue stirring, add 20g of powdered aminosulfonic acid several times during the stirring process, and the aminosulfonic acid addition process lasts for 4h, then add anhydrous ethanol at a constant temperature of 70°C and stir to promote the dissolution of the product, and vacuum filter; adjust the pH value of the filtrate to 7.5-8.5 with a sodium hydroxide solution with a mass fraction of 30%, then filter, and remove ethanol using a rotary evaporator; dry in a vacuum drying oven at 70°C for 12h to obtain cardanol polyoxyethylene ether sulfate; 30g of acetic acid and 30g of triethanolamine were added to 700g of water and stirred evenly. 400g of cardanol polyoxyethylene ether sulfate was added thereto and stirred at a speed of 2000r / min for 2h to obtain a prefabricated material. a ; S2, add 100g of caprolactam to 600g of water and stir evenly, add 150g of rhamnolipid, 20g of polyvinyl pyrrolidone, and 20g of citric acid acylated modified chitosan thereto, stir at a speed of 2000r / min for 2h, and obtain a prefabricated material b ; S3. Add 100g of mesoporous silica with an average particle size of 80nm to 600g of 70% ethanol aqueous solution and stir evenly, add 30g of saturated ammonia water and stir for 20min, add 50g of tetraethyl orthosilicate dropwise under stirring, ultrasonically treat for 5h after complete addition, the ultrasonic frequency is 12kHz, centrifuge, wash with deionized water, vacuum dry, add to 400g of tetrahydrofuran, add 1g of potassium methoxide and stir for 2h, add 100g of dioxane, adjust the system temperature to 90℃, add 20g of glycidol and stir for 2h, the stirring speed is 2000r / min, add 1g of succinic anhydride, stir for 4h under nitrogen protection, add 1000g of ethanol and stir for 2h, centrifuge, wash with ethanol 3 times, vacuum dry, and obtain a prefabricated material. c ; S4, 1100g prefabricated material a Add to 900g prefabricated material b Stir at 2000r / min for 30min, then add 20g prefabricated material c Mix evenly, adjust the pH value of the system to 5-6 with an 8% mass fraction sulfuric acid aqueous solution, add cashmere wool fiber with a bath ratio of 1:50, keep warm at 10℃ for 20min, increase the temperature to 50℃, keep warm for 20min, add 100g acid dye MG-R1 and 20g anhydrous sodium sulfate, stir evenly, keep warm for 2h, increase the temperature to 90℃, keep warm for 50min, take out, wash with water, and dry at room temperature.

[0033] Example 3 A cashmere fiber acid dyeing and fixing method comprises the following steps: S1. Stir 70g of cardanol polyoxyethylene ether (CXF-10) and 1.4g of urea evenly, heat to 120°C and continue stirring, add 19.4g of powdered aminosulfonic acid several times during the stirring process, and the aminosulfonic acid addition process lasts for 200min, then add anhydrous ethanol at a constant temperature of 70°C and stir to promote the dissolution of the product, and vacuum filter; adjust the pH value of the filtrate to 7.5-8.5 with a sodium hydroxide solution with a mass fraction of 30%, then filter, and remove ethanol using a rotary evaporator; dry in a vacuum drying oven at 70°C for 12h to obtain cardanol polyoxyethylene ether sulfate; 25g of acetic acid and 15g of triethanolamine were added to 650g of water and stirred evenly. 250g of cardanol polyoxyethylene ether sulfate was added thereto and stirred at a speed of 1800r / min for 80min to obtain a prefabricated material. a ; S2, 90g of caprolactam was added to 450g of water and stirred evenly, 120g of rhamnolipid, 13g of polyvinyl pyrrolidone, and 18g of citric acid acylated modified chitosan were added thereto, and stirred at a speed of 1300r / min for 100min to obtain a prefabricated material. b ; S3. Add 70g of mesoporous silica with an average particle size of 160nm to 400g of 66% ethanol aqueous solution and stir evenly, add 15g of saturated ammonia water and stir for 18min, add 20g of tetraethyl orthosilicate dropwise under stirring, ultrasonically treat for 4h after complete addition, the ultrasonic frequency is 6kHz, centrifuge, wash with deionized water, vacuum dry, add to 350g of tetrahydrofuran, add 0.3g of potassium methoxide and stir for 100min, add 70g of dioxane, adjust the system temperature to 88°C, add 13g of glycidol and stir for 100min, the stirring speed is 1300r / min, add 0.8g of succinic anhydride, stir for 2.5h under nitrogen protection, add 1800g of ethanol and stir for 80min, centrifuge, wash twice with ethanol, vacuum dry to obtain a prefabricated material c ; S4, 1000g prefabricated material a Add to 600g prefabricated material b Stir at 1700r / min for 15min, then add 17g prefabricated material c Mix evenly, adjust the pH value of the system to 5-6 with a 6% mass fraction sulfuric acid aqueous solution, add cashmere wool fiber with a bath ratio of 1:50, keep warm at 9°C for 12 minutes, increase the temperature to 48°C, keep warm for 13 minutes, add 90g of acid dye MG-R1 and 13g of anhydrous sodium sulfate, stir evenly, keep warm for 100 minutes, increase the temperature to 82°C, keep warm for 45 minutes, take out, wash with water, and dry at room temperature.

[0034] Example 4 A cashmere fiber acid dyeing and fixing method comprises the following steps: S1. Stir 75g of cardanol polyoxyethylene ether (CXF-10) and 1.3g of urea evenly, heat to 140°C and continue stirring, add 19.4g of powdered aminosulfonic acid several times during the stirring process, and the aminosulfonic acid addition process lasts for 220min, then add anhydrous ethanol at a constant temperature of 70°C and stir to promote the dissolution of the product, and vacuum filter; adjust the pH value of the filtrate to 7.5-8.5 with a sodium hydroxide solution with a mass fraction of 30%, then filter, and remove ethanol using a rotary evaporator; dry in a vacuum drying oven at 70°C for 12h to obtain cardanol polyoxyethylene ether sulfate; 15g of acetic acid and 25g of triethanolamine were added to 550g of water and stirred evenly. 350g of cardanol polyoxyethylene ether sulfate was added thereto and stirred at a speed of 1200r / min for 100min to obtain a prefabricated material. a ; S2, add 70g of caprolactam into 550g of water and stir evenly, add 80g of rhamnolipid, 17g of polyvinyl pyrrolidone, and 12g of citric acid acylated modified chitosan thereto, stir at a speed of 1700r / min for 80min, and obtain a prefabricated material b ; S3. Add 90g of mesoporous silica with an average particle size of 100nm to 500g of 64% ethanol aqueous solution and stir evenly, add 25g of saturated ammonia water and stir for 12min, add 40g of tetraethyl orthosilicate dropwise under stirring, ultrasonically treat for 3h after complete addition, the ultrasonic frequency is 9kHz, centrifuge, wash with deionized water, vacuum dry, add to 250g of tetrahydrofuran, add 0.7g of potassium methoxide and stir for 80min, add 90g of dioxane, adjust the system temperature to 82°C, add 17g of glycidol and stir for 80min, the stirring speed is 1700r / min, add 0.2g of succinic anhydride, stir for 3.5h under nitrogen protection, add 1200g of ethanol and stir for 100min, centrifuge, wash twice with ethanol, vacuum dry to obtain a prefabricated material c ; S4, 800g prefabricated material a Add to 800g prefabricated material b Stir at 1300r / min for 25min, then add 13g preform cMix evenly, adjust the pH value of the system to 5-6 with a 7% mass fraction of sulfuric acid aqueous solution, add cashmere wool fiber, the bath ratio is 1:50, keep warm at 7°C for 18 minutes, heat to 42°C, keep warm for 17 minutes, add 70g of acid dye MG-R1 and 17g of anhydrous sodium sulfate, stir evenly, keep warm for 80 minutes, heat to 88°C, keep warm for 35 minutes, take out, wash with water, and dry at room temperature.

[0035] Example 5 A cashmere fiber acid dyeing and fixing method comprises the following steps: S1. Stir 72.5g of cardanol polyoxyethylene ether (CXF-10) and 1.35g of urea evenly, heat to 130°C and continue stirring, add 19.4g of powdered aminosulfonic acid several times during the stirring process, and the aminosulfonic acid addition process lasts for 210min, then add anhydrous ethanol at a constant temperature of 70°C and stir to promote the dissolution of the product, and vacuum filter; adjust the pH value of the filtrate to 7.5-8.5 with a sodium hydroxide solution with a mass fraction of 30%, then filter, and remove ethanol using a rotary evaporator; dry in a vacuum drying oven at 70°C for 12h to obtain cardanol polyoxyethylene ether sulfate; 20g of acetic acid and 20g of triethanolamine were added to 600g of water and stirred evenly. 300g of cardanol polyoxyethylene ether sulfate was added thereto and stirred at a speed of 1500r / min for 90min to obtain a prefabricated material. a ; S2, 80g of caprolactam was added to 500g of water and stirred evenly, 100g of rhamnolipid, 15g of polyvinyl pyrrolidone, and 15g of citric acid acylated modified chitosan were added thereto, and stirred at a speed of 1500r / min for 90min to obtain a prefabricated material. b ; S3. Add 80g of mesoporous silica with an average particle size of 120nm to 450g of 65% ethanol aqueous solution and stir evenly, add 20g of saturated ammonia water and stir for 15min, add 30g of tetraethyl orthosilicate dropwise under stirring, ultrasonically treat for 3.5h after complete addition, the ultrasonic frequency is 7.5kHz, centrifuge, wash with deionized water, vacuum dry, add to 300g of tetrahydrofuran, add 0.5g of potassium methoxide and stir for 90min, add 80g of dioxane, adjust the system temperature to 85°C, add 15g of glycidol and stir for 90min, the stirring speed is 1500r / min, add 0.5g of succinic anhydride, stir for 3h under nitrogen protection, add 1500g of ethanol and stir for 90min, centrifuge, wash twice with ethanol, vacuum dry to obtain a prefabricated material c ; S4, 900g prefabricated material a Add to 700g prefabricated material bStir at 1500r / min for 20min, then add 15g prefabricated material c Mix evenly, adjust the pH value of the system to 5-6 with a 6.5% mass fraction sulfuric acid aqueous solution, add cashmere fiber with a bath ratio of 1:50, keep warm at 8°C for 15 minutes, increase the temperature to 45°C, keep warm for 15 minutes, add 80g of acid dye MG-R1 and 15g of anhydrous sodium sulfate, stir evenly, keep warm for 90 minutes, increase the temperature to 85°C, keep warm for 40 minutes, take out, wash with water, and dry at room temperature.

[0036] The cashmere wool fibers obtained in this embodiment after dyeing and fixing are woven into a fabric such as Figure 1 shown.

[0037] Comparative Example 1 A cashmere fiber acid dyeing and fixing method comprises the following steps: S1. Stir 72.5g of cardanol polyoxyethylene ether (CXF-10) and 1.35g of urea evenly, heat to 130°C and continue stirring, add 19.4g of powdered aminosulfonic acid several times during the stirring process, and the aminosulfonic acid addition process lasts for 210min, then add anhydrous ethanol at a constant temperature of 70°C and stir to promote the dissolution of the product, and vacuum filter; adjust the pH value of the filtrate to 7.5-8.5 with a sodium hydroxide solution with a mass fraction of 30%, then filter, and remove ethanol using a rotary evaporator; dry in a vacuum drying oven at 70°C for 12h to obtain cardanol polyoxyethylene ether sulfate; 20g of acetic acid and 20g of triethanolamine were added to 600g of water and stirred evenly. 300g of cardanol polyoxyethylene ether sulfate was added thereto and stirred at a speed of 1500r / min for 90min to obtain a prefabricated material. a ; S2, 80g of caprolactam was added to 500g of water and stirred evenly, 100g of rhamnolipid, 15g of polyvinyl pyrrolidone, and 15g of citric acid acylated modified chitosan were added thereto, and stirred at a speed of 1500r / min for 90min to obtain a prefabricated material. b ; S3, 900g prefabricated material a Add to 700g prefabricated material b , stirred at a speed of 1500r / min for 20min, then added 15g of mesoporous silica with an average particle size of 120nm and mixed evenly, used a 6.5% mass fraction of sulfuric acid aqueous solution to adjust the pH value of the system to 5-6, added cashmere wool fiber, the bath ratio was 1:50, kept warm at 8℃ for 15min, raised to 45℃, kept warm for 15min, added 80g of acid dye MG-R1 and 15g of anhydrous sodium sulfate, stirred evenly, kept warm for 90min, raised to 85℃, kept warm for 40min, took out, washed with water, and dried at room temperature.

[0038] Comparative Example 2 A cashmere fiber acid dyeing and fixing method comprises the following steps: S1. Stir 72.5g of cardanol polyoxyethylene ether (CXF-10) and 1.35g of urea evenly, heat to 130°C and continue stirring, add 19.4g of powdered aminosulfonic acid several times during the stirring process, and the aminosulfonic acid addition process lasts for 210min, then add anhydrous ethanol at a constant temperature of 70°C and stir to promote the dissolution of the product, and vacuum filter; adjust the pH value of the filtrate to 7.5-8.5 with a sodium hydroxide solution with a mass fraction of 30%, then filter, and remove ethanol using a rotary evaporator; dry in a vacuum drying oven at 70°C for 12h to obtain cardanol polyoxyethylene ether sulfate; 20g of acetic acid and 20g of triethanolamine were added to 600g of water and stirred evenly. 300g of cardanol polyoxyethylene ether sulfate was added thereto and stirred at a speed of 1500r / min for 90min to obtain a prefabricated material. a ; S2, 80g of caprolactam was added to 500g of water and stirred evenly, 100g of rhamnolipid, 15g of polyvinyl pyrrolidone, and 15g of citric acid acylated modified chitosan were added thereto, and stirred at a speed of 1500r / min for 90min to obtain a prefabricated material. b ; S3. Add 80g of mesoporous silica with an average particle size of 120nm to 450g of 65% ethanol aqueous solution and stir evenly, add 20g of saturated ammonia water and stir for 15min, add 30g of tetraethyl orthosilicate dropwise under stirring, ultrasonically treat for 3.5h after complete addition, the ultrasonic frequency is 7.5kHz, centrifuge, wash with deionized water, vacuum dry, add to 300g of tetrahydrofuran, add 0.5g of potassium methoxide and stir for 90min, add 80g of dioxane, adjust the system temperature to 85°C, add 15g of glycidol and stir for 90min, the stirring speed is 1500r / min, add 0.5g of succinic anhydride, stir for 3h under nitrogen protection, add 1500g of ethanol and stir for 90min, centrifuge, wash twice with ethanol, vacuum dry to obtain a prefabricated material c ; S4, 900g prefabricated material a Add to 700g prefabricated material b Stir at 1500r / min for 20min, then add 15g prefabricated material c, 80g of acid dye MG-R1 are mixed evenly, and the pH value of the system is adjusted to 5-6 with a 6.5% mass fraction of sulfuric acid aqueous solution, and cashmere fiber is added thereto with a bath ratio of 1:50. The temperature is kept at 8°C for 15 minutes, the temperature is increased to 45°C, and the temperature is kept for 15 minutes. 15g of anhydrous sodium sulfate is added and stirred evenly, and the temperature is kept for 90 minutes. The temperature is increased to 85°C, and the temperature is kept for 40 minutes. Take out, wash with water, and dry at room temperature.

[0039] The desizing rates of the dyed and fixed cashmere fibers obtained in Example 5 and Comparative Examples 1-2 were measured.

[0040] Desizing rate = (cashmere fiber mass before desizing - cashmere fiber mass after desizing) ÷ cashmere fiber mass before desizing × 100% K / S is a commonly used calculation formula for measuring the color depth of an object surface, which represents the absorption coefficient of the object being measured. The depth of fabric dyeing is measured by testing the K / S value. The depth of dyeing is one of the important indicators for evaluating dyeing performance. Among them, K is the absorption coefficient of the object being measured, and S is the scattering coefficient of the object being measured.

[0041] The K / S value of the dyed and fixed cashmere fibers obtained in Example 5 and Comparative Examples 1-2 was measured under standard light source D65 using a Datacolor SF600 Plus spectrophotometer. The sample was folded in half twice, and the measurement was performed four times at different positions to obtain the average value. The larger the K / S value, the darker the surface color of the sample.

[0042] like Figure 2 As shown, the desizing rates of the three groups of cashmere wool fibers after dyeing and fixing were all greater than 80%, and the desizing rate of the cashmere wool fibers after dyeing and fixing obtained in Example 5 was the highest, which was better than that of Comparative Examples 1-2 (P>0.05). At the same time, the K / S value of the cashmere wool fibers after dyeing and fixing obtained in Example 5 was the highest, proving that the method of Example 5 can improve the dyeing efficiency at the same temperature and time.

[0043] The dye uptake and fixation rates of the cashmere wool fibers obtained in Example 5 and Comparative Examples 1-2 after dyeing and fixation were measured.

[0044] Dyeing rate = (total mass of dye - mass of dye remaining in the residual liquid after cashmere fiber dyeing) ÷ total mass of dye × 100% Fixation rate = (total dye mass - residual dye mass in the residual liquid after cashmere wool fiber dyeing - residual dye mass in the soaping liquid after cashmere wool fiber dyeing) ÷ total dye mass × 100% like Figure 3 As shown, the dyeing rate and fixation rate of the cashmere wool fiber after dyeing and fixation obtained in Example 5 are the highest, which are better than those of Comparative Examples 1-2 (P>0.05).

[0045] The undyed and fixed cashmere fibers and the dyed and fixed cashmere fibers obtained in Example 5 and Comparative Examples 1-2 were balanced under the secondary standard atmosphere for 24 hours, and then the strength was measured. The tensile speed was 50 mm / min, the clamp spacing was 250 mm, 50 fibers were randomly selected from each group for testing, and the test results were averaged to calculate the strength retention rate of the dyed and fixed cashmere fibers obtained in Example 5 and Comparative Examples 1-2.

[0046] Strength retention rate = Example 5 / Comparative Example 1 / Comparative Example 2 Strength of cashmere wool fiber after dyeing and fixing / undyed and fixed cashmere wool fiber × 100% like Figure 4 As shown, the cashmere wool fiber obtained in Example 5 has the highest strength retention rate after dyeing and fixation.

[0047] The color fastness to dry / wet rubbing of the cashmere wool fibers obtained in Example 5 and Comparative Examples 1-2 after dyeing and fixing was evaluated with reference to GB / T 3920-2008 "Textiles - Tests for Color Fastness - Color Fastness to Rubbing". The color fastness to soaping of the cashmere wool fibers obtained in Example 5 and Comparative Examples 1-2 after dyeing and fixing was evaluated with reference to GB / T 3921-2008 "Textiles - Tests for Color Fastness - Color Fastness to Washing". The color fastness to water of the cashmere wool fibers obtained in Example 5 and Comparative Examples 1-2 after dyeing and fixing was evaluated with reference to GB / T 5713-2013 "Textiles - Tests for Color Fastness - Color Fastness to Water".

[0048] like Figure 5 As shown, the color fastness of each group is ≥ level 4, which proves that the cashmere wool fibers dyed and fixed by the method of Example 5 or Comparative Examples 1-2 have high resistance to various fading effects. The color fastness of the cashmere wool fibers after dyeing and fixing obtained in Example 5 is all level 5, which is better than Comparative Examples 1-2.

[0049] The applicant believes that this is because the present invention deposits nano-silica on mesoporous silica, grafts hyperbranched structures and then performs carboxyl functionalization, which is not only more conducive to the entry of acid dyes, but also realizes efficient loading of dyes due to its high specific surface area and pore volume, and has high stability due to the steric hindrance effect of the hyperbranched structure and the terminal carboxyl functional group. a , Prefabricated materials b Prepare dyeing auxiliary agent, and then prepare the prefabricated material c Add to dyeing auxiliaries, then add cashmere wool fibers to it, pre-made c The active carboxyl group at the end can be combined with the surface of cashmere fiber structure, improving the binding degree between acid dye and cashmere fiber, thereby increasing the dye uptake rate and dye fastness. At the same time, the fiber strength is high and the mechanical property loss is small. cFirst, it is combined with cashmere fibers, and then acid dyes are added. At low temperatures, it can effectively delay the rapid dyeing of acid dyes. As the temperature rises, the acid dyes are evenly adsorbed, effectively preventing the dyes from quickly dyeing the fibers. The combined effect of triethanolamine and caprolactam can better dissolve the acid dyes and further enhance the uniformity of dye coloring on the fibers.

[0050] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for fixing the acid dyeing of cashmere wool fibers, characterized in that: The steps include: S1. Add acetic acid and triethanolamine to water and stir evenly, add cardanol polyoxyethylene ether sulfate and stir for 1-2h to obtain a prefabricated material. a ; S2. Add caprolactam into water and stir evenly, add rhamnolipid, polyvinyl pyrrolidone and acylated modified chitosan into water and stir for 1-2h to obtain prefabricated material. b ; S3, adding mesoporous silica to ethanol aqueous solution and stirring evenly, adding saturated ammonia water thereto and stirring for 10-20 minutes, adding tetraethyl orthosilicate thereto dropwise while stirring, ultrasonically treating after complete addition, centrifuging, washing, drying, adding to tetrahydrofuran, adding potassium methoxide and stirring for 1-2 hours, adding dioxane, adjusting the system temperature to 80-90°C, adding glycidol and stirring for 1-2 hours, adding succinic anhydride, stirring for 2-4 hours under nitrogen protection, adding ethanol and stirring for 1-2 hours, centrifuging, washing, and vacuum drying to obtain a preform c ; S4, prefabricated material a Add to preform b Stir for 10-30 minutes, then add the prefabricated material c Mix evenly, adjust the pH value of the system to 5-6, add cashmere fiber, keep warm at 5-10℃ for 10-20min, increase the temperature to 40-50℃, keep warm for 10-20min, add acid dye and anhydrous sodium sulfate, stir evenly, keep warm for 1-2h, increase the temperature to 80-90℃, keep warm for 30-50min, take out, wash with water, and dry at room temperature.

2. The method for fixing cashmere fiber acid dyeing according to claim 1, characterized in that: In S1, cardanol polyoxyethylene ether sulfate is obtained by reacting cardanol polyoxyethylene ether with aminosulfonic acid using urea as a catalyst.

3. The method for fixing cashmere fiber acid dyeing according to claim 1, characterized in that: In S1, the mass ratio of acetic acid, triethanolamine and cardanol polyoxyethylene ether sulfate is 1-3:1-3:20-40.

4. The method for fixing cashmere fiber acid dyeing according to claim 1, characterized in that: In S2, the mass ratio of caprolactam, rhamnolipid, polyvinyl pyrrolidone and acylated modified chitosan is 5-10:5-15:1-2:1-2.

5. The method for fixing cashmere fiber acid dyeing according to claim 1, characterized in that: In S3, the mesoporous silica particle size is 50-200 nm.

6. The method for fixing cashmere fiber acid dyeing according to claim 1, characterized in that: In S3, the mass ratio of mesoporous silica, saturated ammonia water, ethyl orthosilicate, potassium methoxide, dioxane, glycidol, and succinic anhydride is 5-10: 1-3: 1-5: 0.01-0.1: 5-10: 1-2: 0.01-0.

1.

7. The method for fixing cashmere fiber acid dyeing according to claim 1, characterized in that: In S3, the mass fraction of the ethanol aqueous solution is 60-70%.

8. The method for fixing cashmere fiber acid dyeing according to claim 1, characterized in that: In S4, prefabricated a , Prefabricated materials b , Prefabricated materials c The mass ratio of acid dye and anhydrous sodium sulfate is 70-110:50-90:1-2:5-10:1-2.

9. The method for fixing cashmere fiber acid dyeing according to claim 1, characterized in that: In S4, cashmere wool fibers are added to make the bath ratio of the system 1:

50.

10. The method for fixing cashmere fiber acid dyeing according to claim 1, characterized in that: In S4, a sulfuric acid aqueous solution with a mass fraction of 5-8% is used to adjust the pH value of the system to 5-6.

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