A finishing method for simultaneous in-situ dyeing and flame retardancy
By catalyzing the copolymerization of plant phenols and organophosphorus compounds through laccase, the problem of damage to protein fibers caused by traditional dyeing and flame retardant methods is solved, and simultaneous dyeing and flame retardancy are achieved under mild conditions, which improves the color fastness and flame retardant durability of the fabric and maintains the feel and mechanical properties of the fiber.
Patent Information
- Application Number
- CN202411149272.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-21
- Publication Date
- 2025-09-09
- Estimated Expiration
- 2044-08-21
AI Technical Summary
Traditional dyeing and flame retardant methods cause great damage to protein fiber fabrics and are energy- and water-intensive, making it difficult to achieve environmentally friendly and efficient simultaneous finishing.
Laccase is used to catalyze the copolymerization of plant phenols and organophosphorus compounds, and simultaneous dyeing and flame retardancy are achieved on protein fibers through in situ reaction. The catalytic oxidation effect of laccase is utilized to make plant phenols and organophosphorus compounds copolymerize and cross-link on protein fibers, forming a stable dyeing and flame retardant effect.
It achieves simultaneous dyeing and flame retardancy under mild conditions, improves the color fastness and flame retardancy durability of the fabric, reduces harm to the environment and human body, and maintains the feel and mechanical properties of the fiber.
Smart Images
Figure CN118910904B_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of simultaneous dyeing and flame retardancy, and particularly relates to a finishing method for simultaneous in-situ dyeing and flame retardancy. Background Art
[0002] Protein fibers in the textile industry primarily include silk and wool. These fibers possess excellent moisture absorption and breathability, making them suitable for use in clothing and home textiles. In recent years, with economic development, wigs have become increasingly popular among those seeking beauty. Human hair wigs, considered healthier and more comfortable, are highly sought after by consumers. Human hair, similar in physical and chemical structure to wool, is also a protein fiber. Traditional dyeing and flame-retardant treatments for protein fiber fabrics require demanding conditions. These methods typically require high temperatures, consume significant amounts of energy, and damage the fiber or fabric. The dyeing process also consumes significant amounts of chemicals.
[0003] Durable flame retardancy of protein fibers and fabrics is typically achieved by high-temperature baking using phosphorus-containing compounds in the presence of a crosslinking agent. Wool fabrics can also be treated with metal complexes such as potassium hexafluorotitanate. However, these finishing methods can lead to yellowing, damage to the fabric, or heavy metal contamination. Consequently, the search for environmentally friendly and efficient methods for dyeing and flame-retardant finishing of protein fibers has attracted increasing research attention. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to provide a finishing method that achieves both in-situ dyeing and flame retardancy simultaneously, utilizing laccase, plant phenol and organophosphorus copolymerization and reacting with the material to be finished to simultaneously impart color and flame retardancy to the material. The method is simple and feasible. The technical solution adopted is:
[0005] A finishing method for simultaneously achieving in-situ dyeing and flame retardancy comprises the following steps:
[0006] (1) Add methanol / acetic acid-sodium acetate buffer solution as solvent to an Erlenmeyer flask, and place the Erlenmeyer flask in an oscillating water bath and heat to 50-80°C;
[0007] (2) Add plant phenol, organophosphorus compound, and laccase to a conical flask in sequence, shake well to obtain a mixed solution, and then add the object to be processed;
[0008] (3) Oscillate the conical flask, maintain the water bath temperature at 50-80°C, and continue the reaction;
[0009] (4) After the reaction is completed, the material to be processed is soaked and washed with warm water and cold water, and then dried.
[0010] Preferably, the material to be finished is any one or more of wool fiber fabric, silk fabric and human hair fiber.
[0011] Preferably, the mass concentration of methanol in the solvent methanol / acetic acid-sodium acetate buffer solution is 5-20%; and its pH is 4-6.
[0012] Preferably, the plant phenols are phenolic acids, flavonoids and lignins, etc.; the organophosphorus compounds are organophosphorus compounds containing PH bonds.
[0013] Preferably, the plant phenol is any one of gallic acid, tea polyphenols, and tannin; the organophosphorus compound containing a PH bond is any one of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), dimethyl phosphite, and diethyl phosphite.
[0014] Preferably, the activity of laccase in the mixed solution uniformly mixed in step (2) is 0.1-5 U / mL.
[0015] Preferably, the molar ratio of plant phenol to organophosphorus compound in the mixed solution in step (2) is 1:1 to 2.5.
[0016] Preferably, in step (3), the reaction time is 8 to 24 hours.
[0017] Preferably, in step (4), the warm water is water at 50-60°C, and the cold water is water at 0-10°C.
[0018] Preferably, the soaking time in warm water and cold water is 20 to 30 minutes; finally, the product is washed with cold water for 3 to 5 times and dried in an oven at 40 to 60°C.
[0019] Compared with the prior art, the present invention has the following beneficial effects:
[0020] The present invention proposes a method for simultaneously achieving in-situ dyeing and flame retardancy, and a method for durable in-situ dyeing and flame retardancy simultaneous finishing. The process is simple, using plant phenols and organophosphorus compounds as catalytic substrates, and utilizing the catalytic oxidation of laccase to copolymerize the plant phenols and organophosphorus compounds to produce color, and then react with wool fiber fabrics, silk fabrics, and human hair fibers, successfully imparting dyeing and flame retardancy without affecting the hand feel, and can also enhance the breaking strength of the fibers or fabrics.
[0021] Using laccase as a catalyst can achieve simultaneous finishing of dyeing and flame retardant functions. The process is simple and avoids the problems of water consumption, energy consumption, pollution and fiber or fabric damage caused by traditional dyeing and flame retardant finishing.
[0022] Plant phenols or organophosphorus compounds form a stable cross-linking grafting effect with protein fibers / fabrics, which greatly improves the color fastness of dyed fabrics and the washability of the flame retardant effect.
[0023] Organophosphorus compounds have good stability and do not release large amounts of toxic gases or smoke during combustion, reducing harm to the environment and human body.
[0024] The enzyme-catalyzed polymerization reaction conditions are mild. Compared with traditional chemical dyeing and flame retardant modification methods, this process causes less damage to protein fibers. The protein fibers after dyeing and flame retardant modification can still maintain their original soft and fluffy feel. At the same time, the cross-linking effect of plant phenols inside the protein fibers significantly improves the mechanical properties of the fabric. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Figure 1 The dyeing pictures of the blank wool fabric (a) and the wool fabric treated according to Example 1 of the present invention (b) are compared.
[0026] Figure 2 Comparison of dyeing pictures of a blank silk fabric (a) and a silk fabric treated with Example 3 of the present invention (b).
[0027] Figure 3 Comparison of blank dyed hair (a) and dyed human hair (b) treated by Example 4 of the present invention.
[0028] Figure 4 This is a graph showing the changes in the flame retardant properties of human hair, where a: original hair exposed to flame for 1 second; b: original hair ignited for 10 seconds; c: treated hair ignited for 1 second; d: treated hair ignited for 10 seconds. DETAILED DESCRIPTION
[0029] The accompanying drawings are for illustrative purposes only. The present invention will be described in detail below with reference to the accompanying drawings. Unless otherwise specified in the present invention, the raw materials used can be purchased through conventional commercial channels.
[0030] Example 1
[0031] Add 200 mL of methanol / acetic acid-sodium acetate buffer solution solvent (methanol mass concentration: 10%; pH = 5) to a conical flask, place the conical flask in an oscillating water bath, and raise the temperature to 50°C; then add 5 g of gallic acid, 5 g of DOPO, and 2.87 g of laccase in sequence, mix well, and add 4 g of wool fabric; oscillate the conical flask, maintain the water bath temperature at 50°C, and react for 12 hours; after the reaction is completed, soak and wash the wool fabric with warm water and then cold water, and then dry it.
[0032] The LOI (Limiting Oxygen Index) of the finished fabric was tested according to GB / T5454-1997 "Textiles Test for Burning Behavior: Oxygen Index Method". The results are shown in Table 1.
[0033] Table 1 Comparison of dyeing effect and flame retardant effect of wool fabric before and after treatment
[0034] sample Blank wool fabric Finished wool fabric K / S(360nm) 1.18 5.92 LOI (%) 26.0 27.5
[0035] Through Table 1 and Figure 1 It can be seen that the dyeing effect and flame retardant effect of the wool fabric after being finished in the embodiment are significantly improved.
[0036] Dyed and flame-retardant modified wool fabrics were washed according to AATCC-61, "Color Fastness to Washing: Rapid Method." The specific process is as follows: Samples were immersed in a 0.15% AATCC standard detergent solution in water and washed at 49°C for 45 minutes with shaking (this process constitutes one wash cycle, equivalent to five home washes). One sample was removed after each cycle, dried, and then tested for surface color depth (K / S value) and flammability (LOI value) to characterize the changes in the dyeing and flame-retardant properties of the fabrics after different wash cycles. Table 2 shows the effect of wash cycles on the dyeing and flame-retardant properties of the dyed and flame-retardant wool fabrics.
[0037] Table 2 Effect of washing times on dyeing and flame retardant properties of wool fabrics
[0038] Washing times 0 5 10 15 20 25 K / S(360nm) 5.92 5.62 5.36 5.26 5.21 5.19 LOI (%) 27.5 27.3 27.3 27.2 27.2 27.2
[0039] According to GB / T5454-1997, when the LOI of a fabric is ≥26%, it is considered a flame retardant material. From the results in Table 2, it can be seen that the LOI of the fabric is still 27.2% after 25 washes. Therefore, the wool fabric treated by the method of the present invention has good flame retardancy and durability.
[0040] Example 2
[0041] Add 200 mL of methanol / acetic acid-sodium acetate buffer solution solvent (methanol mass concentration: 10%; pH = 5) to a conical flask, place the conical flask in an oscillating water bath, and raise the temperature to 50°C; then add 20 g of tea polyphenols, 20 g of DOPO, and 2.87 g of laccase in sequence, mix well, and add 4 g of wool fabric; oscillate the conical flask, maintain the water bath temperature at 50°C, and react for 24 hours; after the reaction, soak and wash the silk fabric with warm water and cold water, and then dry it.
[0042] The LOI (Limiting Oxygen Index) of the treated fabrics was tested according to GB / T5454-1997, "Textiles Test for Combustion Behavior: Oxygen Index Method." The results are shown in Table 3. Table 3 compares the dyeing and flame retardant properties of the treated wool fabrics before and after treatment. The dyeing and flame retardant properties of the treated wool fabrics were superior to those of the untreated wool fabrics.
[0043] Table 3 Comparison of dyeing effect and flame retardant effect of silk fabrics before and after treatment
[0044] sample Blank wool fabric Finished wool fabric K / S(360nm) 1.18 6.68 LOI (%) 26.0 29.1
[0045] Example 3
[0046] Add 200 mL of methanol / acetic acid-sodium acetate buffer solution solvent (methanol mass concentration: 10%; pH = 5) to a conical flask, place the conical flask in a shaking water bath, and raise the temperature to 50°C; then add 10 g of gallic acid, 10 g of DOPO, and 2.87 g of laccase in sequence, mix well, and add 4 g of silk fabric; shake the conical flask, maintain the water bath temperature at 50°C, and react for 12 hours; after the reaction, soak and wash the silk fabric with warm water and then cold water, and dry it.
[0047] The LOI (Limiting Oxygen Index) of the finished fabric was tested according to GB / T5454-1997 "Textiles Burning Behavior Test: Oxygen Index Method". The results are shown in Table 4.
[0048] Table 4 Comparison of dyeing effect and flame retardant effect of silk fabrics before and after treatment
[0049] sample Blank silk fabric Finished silk fabric K / S(360nm) 0.35 3.68 LOI (%) 24.5 26.2
[0050] according to Figure 2 As shown in Table 4, compared with the untreated blank silk fabric, the silk fabric treated in Example 3 has improved dyeing effect and flame retardant effect.
[0051] Example 4
[0052] Add 200 mL of methanol / acetic acid-sodium acetate buffer solution solvent (methanol mass concentration: 10%; pH = 5) to a conical flask, place the conical flask in a shaking water bath, and raise the temperature to 50°C; then add 5 g of gallic acid, 5 g of DOPO, and 2.87 g of laccase in sequence, mix well, and add 4 g of human hair fiber; shake the conical flask, maintain the water bath temperature at 50°C, and react for 12 hours; after the reaction, soak and wash the human hair with warm water and then cold water, and dry it.
[0053] The color characteristic values (K / S) of human hair before and after treatment were measured using a Data color spectrophotometer (D65 light source, 10° field of view) with a large aperture (30 mm). The measurement position of each sample was randomly changed and the average value was calculated after multiple measurements to obtain the K / S values of different dyed samples. Figure 3 Table 5 shows the K / S values of human hair fibers before and after treatment and the dyeing effect diagram.
[0054] Table 5 Comparison of dyeing effects of human hair fabrics before and after treatment
[0055] sample Blank human hair fiber Finished human hair fibers K / S(360nm) 7.01 18.13
[0056] Depend on Figure 3 As shown in Table 5, the dyeing effect of the human hair fibers treated in Example 4 is improved compared with the untreated blank human hair fibers.
[0057] like Figure 4 As shown, human hair fibers are not suitable for limited oxygen index testing in their current state. Therefore, the present invention compares the vertical combustion performance of human hair before and after treatment to characterize the changes in flame retardancy. Figure a shows the original (i.e., a blank human hair fiber sample) exposed to flame for 1 second, with no noticeable dyeing and the base just beginning to burn. Figure b shows the original sample 10 seconds after ignition, with noticeable burning but not vertical. Figure c shows the human hair sample treated with Example 4, 1 second after ignition, maintaining a vertical position even after ignition. Figure d shows the treated sample 10 seconds after ignition, with some burning at the base but maintaining a vertical position, while the upper portion remains unburned, demonstrating that the treated human hair fabric exhibits improved flame retardancy.
[0058] Of course, the above description is not a limitation of the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or substitutions made by technicians in this technical field within the essential scope of the present invention should also fall within the scope of protection of the present invention.
Claims
1. A finishing method for simultaneous in-situ dyeing and flame retardancy, characterized in that: The following steps are involved: (1) Add methanol / acetic acid-sodium acetate buffer solution as solvent to a conical flask, and place the conical flask in a shaking water bath and heat it to 50-80 °C; (2) Add plant phenol, organophosphorus compound, and laccase to a conical flask in sequence, shake well to obtain a mixed solution, and then add the material to be processed; (3) Oscillate the conical flask, maintain the water bath temperature at 50-80 °C, and continue the reaction; (4) After the reaction is completed, soak and wash the material to be treated with warm water and cold water, and then dry it; Wherein, the material to be finished is any one or more of wool fiber fabric, silk fabric and human hair fiber; The plant phenol is any one of gallic acid, tea polyphenols, and tannin; the organophosphorus compound is an organophosphorus compound containing a PH bond, which is any one of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dimethyl phosphite, and diethyl phosphite.
2. The finishing method for simultaneous in-situ dyeing and flame retardancy according to claim 1, characterized in that: The mass concentration of methanol in the solvent methanol / acetic acid-sodium acetate buffer solution is 5-20%; its pH is 4-6.
3. The finishing method for simultaneous in-situ dyeing and flame retardancy according to claim 1, characterized in that: The activity of laccase in the mixed solution uniformly mixed in step (2) is 0.1-5 U / mL.
4. The method for simultaneously achieving in-situ dyeing and flame retardancy according to claim 1, characterized in that: The molar ratio of plant phenol to organophosphorus compound in the mixed solution in step (2) is 1:1 to 2.
5.
5. The finishing method for simultaneous in-situ dyeing and flame retardancy according to claim 1, characterized in that: In the step (3), the reaction time is 8 to 24 hours.
6. The method for simultaneously achieving in-situ dyeing and flame retardancy according to claim 1, characterized in that: In the step (4), the warm water is water at 50-60°C, and the cold water is water at 0-10°C.
7. The method for simultaneously achieving in-situ dyeing and flame retardancy according to claim 6, characterized in that: The soaking time for warm water and cold water is 20~30 minutes; finally, rinse with cold water 3~5 times and dry in an oven at 40~60℃.