Chitosan polyphenol composite spinning method and application of chitosan polyphenol composite spinning method in artificial hair

Abstract

The invention discloses a chitosan polyphenol composite spinning method and application of the chitosan polyphenol composite spinning method in artificial hair, and belongs to the technical field of bio-based spinning. According to the chitosan / punicalagin (CS / PL) colored composite fiber and the preparation method thereof, punicalagin and chitosan are subjected to mixed spinning through a wet spinning method, the chitosan / punicalagin (CS / PL) colored composite fiber is prepared, the degradability, biocompatibility and antibacterial property of chitosan are reserved, the composite fiber can be endowed with natural brown yellow, and the mechanical performance of the fiber is improved. The chitosan / punicalagin composite fiber prepared by the invention has excellent anti-swelling performance, mechanical performance, flexibility and flame retardancy which are obviously superior to those of commercially available artificial hair.

Description

Technical Field

[0001] The present invention relates to a method for composite spinning of chitosan polyphenol and its application in artificial hair, belonging to the technical field of bio-based spinning. Background Art

[0002] Driven by the exacerbation of hair loss problems, the diversification of aesthetic concepts, and personalized consumption demands, artificial hair products, as products with both functional and fashionable attributes, have seen a continuous increase in market demand. Currently, the fibers used to make artificial hair are mainly synthetic fibers such as polyester fibers and nylon fibers, which have problems such as being difficult to degrade, prone to generating static electricity, adsorbing dust, lacking natural luster, and being flammable.

[0003] Chitosan (CS) is the only natural alkaline polysaccharide in nature, second only to cellulose in content, and has characteristics such as biocompatibility, degradability, antibacterial property, and safety, especially suitable for products in contact with the skin. At the same time, it has a high carbon element content, has side chain hydroxyl groups and amino groups, and can be carbonized and release non-toxic and non-flammable gases such as CO2, NH3, and N2 when decomposed by heat, having a certain flame retardant effect. However, CS fibers have poor water stability and mechanical properties and cannot meet the requirements of artificial hair.

[0004] Currently, many technologies modify CS fibers to improve their different properties. Patent CN119113182A prepares composite nanofiber powder with improved mechanical properties by electrospinning silk fibroin and chitosan; Patent CN117210969A uses chitosan composite alginic acid to prepare nanofibers with improved antibacterial and mechanical properties; Patent CN116926969A uses gelatin, tea polyphenols, and chitosan to prepare a blended flocked cloth with improved antibacterial properties; Patent CN101665985A discloses a fiber membrane with broad-spectrum bactericidal properties using tea polyphenols and chitosan. The above patents mainly focus on coatings, food preservation films, etc., and lack in-depth application exploration of the flexibility and combustion performance of the prepared chitosan fibers themselves.

[0005] Therefore, developing a chitosan fiber with excellent properties and applying it to artificial hair products has extremely high practical value and economic value. Summary of the Invention

[0006] To solve the above problems, the present invention uses a wet spinning method to mix and spin punicalagin (PL) with chitosan to prepare a chitosan / punicalagin (CS / PL) colored composite fiber, which not only retains the degradability, biocompatibility, and antibacterial property of chitosan, but also can endow the composite fiber with natural brown-yellow color and improve the mechanical properties of the composite fiber. The chitosan / punicalagin (CS / PL) composite fiber prepared by the present invention has excellent anti-swelling performance, mechanical properties, flexibility, and flame retardant properties, all of which are significantly superior to commercially available artificial hair.

[0007] The first object of the present invention is to provide a method for preparing chitosan / punicalagin composite fibers, comprising the following steps:

[0008] (1) Dissolve chitosan in an aqueous acetic acid solution, add punicalagin, and mix well to obtain a chitosan / punicalagin composite spinning solution;

[0009] Wherein, the final concentration of chitosan in the chitosan / punicalagin composite spinning solution is 1-3% w / w, and the final concentration of punicalagin is 0.05-0.2% w / w;

[0010] (2) Perform wet spinning on the chitosan / punicalagin composite spinning solution and carry out coagulation in a coagulation bath to prepare chitosan / punicalagin composite fibers.

[0011] Optionally, the final concentration of chitosan is 2% w / w, and the final concentration of punicalagin is 0.1% w / w.

[0012] In one embodiment, the coagulation bath in step (2) is obtained by mixing a sodium hydroxide solution and ethanol in a mass ratio of 2-3:1;

[0013] Optionally, the concentration of the sodium hydroxide solution is 3-5% w / w; the solvent is water;

[0014] Optionally, the concentration of the sodium hydroxide solution is 5%;

[0015] Optionally, the ethanol is anhydrous ethanol.

[0016] Optionally, the wet spinning is to inject the chitosan / punicalagin composite spinning solution into the coagulation bath through a needle at a flow rate of 0.4-0.6 mL / min, and after being drawn by two drawing rollers, it is left standing and dried in a glycerol solution to prepare chitosan / punicalagin composite fibers (i.e., CS / PL composite fibers);

[0017] Optionally, the glycerol solution is an aqueous glycerol solution with a concentration of 0.5-1.5% w / w.

[0018] In one embodiment, the concentration of the aqueous acetic acid solution in step (1) is 1-3% w / w;

[0019] Optionally, in step (1), chitosan is dissolved in the aqueous acetic acid solution and stirred at 35-40 °C for 4-6 h.

[0020] In one embodiment, the mixing in step (1) is to stir at 35-40 °C for 2-3 h and then perform ultrasonic treatment at 15-20 kHz for 15-20 min.

[0021] The second object of the present invention is to provide chitosan / punicalagin composite fibers prepared by any of the above methods.

[0022] The third object of the present invention is to provide an application of any of the above methods or the above chitosan / punicalagin composite fiber in the field of functional textiles.

[0023] In one embodiment, the application in the field of functional textiles includes the preparation of clothing, artificial hair, and medical textiles.

[0024] In one embodiment, the application in the field of functional textiles includes, but is not limited to, the preparation of wound dressings, surgical sutures, bed sheets, quilt covers, etc.

[0025] The fourth object of the present invention is to provide a product containing the above chitosan / punicalagin composite fiber.

[0026] In one embodiment, the product includes artificial hair, medical textiles, and clothing.

[0027] In one embodiment, the product includes, but is not limited to, wound dressings, surgical sutures, bed sheets, quilt covers, etc.

[0028] The fifth object of the present invention is to provide an artificial hair, which is prepared from the chitosan / punicalagin composite fiber;

[0029] Wherein, the preparation method of the chitosan / punicalagin composite fiber includes the following steps:

[0030] (1) Dissolve chitosan in an acetic acid aqueous solution, add punicalagin, and mix evenly to obtain a chitosan / punicalagin composite spinning solution;

[0031] Wherein, the final concentration of chitosan in the chitosan / punicalagin composite spinning solution is 1-3% w / w, and the final concentration of punicalagin is 0.05-0.2% w / w;

[0032] (2) Perform wet spinning on the chitosan / punicalagin composite spinning solution and carry out coagulation in a coagulation bath to prepare the chitosan / punicalagin composite fiber;

[0033] Optionally, the concentration of the acetic acid aqueous solution in step (1) is 1-3% w / w;

[0034] Optionally, in step (1), chitosan is dissolved in the acetic acid aqueous solution and stirred at 35-40°C for 4-6 h;

[0035] Optionally, in step (2), the coagulation bath is obtained by mixing a sodium hydroxide solution and ethanol according to a mass ratio of 2-3:1;

[0036] Optionally, the concentration of the sodium hydroxide solution is 3-5% w / w;

[0037] Optionally, in wet spinning, the chitosan / punicalagin composite spinning solution is injected into a coagulation bath through a needle at a flow rate of 0.4 - 0.6 mL / min. After being drawn by two drafting rollers, it is left standing and dried in a glycerol solution to obtain chitosan / punicalagin composite fibers.

[0038] The sixth object of the present invention is to provide a method for preparing artificial hair, and the artificial hair is composed of chitosan / punicalagin composite fibers;

[0039] Among them, the preparation method of the chitosan / punicalagin composite fibers includes the following steps:

[0040] (1) Dissolve chitosan in an acetic acid aqueous solution, add punicalagin, and mix well to obtain a chitosan / punicalagin composite spinning solution;

[0041] Among them, the final concentration of chitosan in the chitosan / punicalagin composite spinning solution is 1 - 3% w / w, and the final concentration of punicalagin is 0.05 - 0.2% w / w;

[0042] (2) Perform wet spinning on the chitosan / punicalagin composite spinning solution and carry out coagulation in a coagulation bath to obtain chitosan / punicalagin composite fibers.

[0043] Optionally, in step (1), the concentration of the acetic acid aqueous solution is 1 - 3% w / w;

[0044] Optionally, in step (1), chitosan is dissolved in the acetic acid aqueous solution and stirred at 35 - 40 °C for 4 - 6 h;

[0045] Optionally, in step (2), the coagulation bath is obtained by mixing a sodium hydroxide solution and ethanol according to a mass ratio of 2 - 3:1;

[0046] Optionally, the concentration of the sodium hydroxide solution is 3 - 5% w / w;

[0047] Optionally, in wet spinning, the chitosan / punicalagin composite spinning solution is injected into a coagulation bath through a needle at a flow rate of 0.4 - 0.6 mL / min. After being drawn by two drafting rollers, it is left standing and dried in a glycerol solution to obtain chitosan / punicalagin composite fibers.

[0048] The seventh object of the present invention is to provide a method for simultaneously improving the mechanical properties, compliance properties, and flame retardant properties of chitosan composite fibers, and the method includes the following steps:

[0049] (1) Dissolve chitosan in an acetic acid aqueous solution, add punicalagin, and mix well to obtain a chitosan / punicalagin composite spinning solution;

[0050] Among them, the final concentration of chitosan in the chitosan / punicalagin composite spinning solution is 1-3% w / w, and the final concentration of punicalagin is 0.05-0.2% w / w;

[0051] (2) Wet spinning the chitosan / punicalagin composite spinning solution and coagulating it in a coagulation bath to prepare chitosan / punicalagin composite fibers.

[0052] Optionally, the final concentration of chitosan is 2% w / w, and the final concentration of punicalagin is 0.1% w / w.

[0053] In one embodiment, the coagulation bath in step (2) is obtained by mixing sodium hydroxide solution and ethanol in a mass ratio of 2-3:1;

[0054] Optionally, the concentration of the sodium hydroxide solution is 3-5% w / w;

[0055] Optionally, the concentration of the sodium hydroxide solution is 5%.

[0056] Optionally, in wet spinning, the chitosan / punicalagin composite spinning solution is injected into the coagulation bath through a needle at a flow rate of 0.4-0.6 mL / min, and after being drawn by two drafting rollers, it is left standing and dried in a glycerol solution to prepare CS / PL composite fibers.

[0057] In one embodiment, the concentration of the acetic acid aqueous solution in step (1) is 1-3% w / w;

[0058] Optionally, in step (1), chitosan is dissolved in the acetic acid aqueous solution and stirred at 35-40 °C for 4-6 h.

[0059] In one embodiment, in step (1), the mixing is carried out by stirring at 35-40 °C for 2-3 h and then ultrasonic treatment at 15-20 kHz for 15-20 min.

[0060] Advantages of the present invention

[0061] The present invention uses the method of wet spinning to mix and spin punicalagin and chitosan to prepare chitosan / punicalagin (CS / PL) colored composite fibers, which not only retain the degradability, biocompatibility and antibacterial properties of chitosan, but also can endow the composite fibers with natural brown-yellow color and improve the mechanical properties of the composite fibers. The chitosan / punicalagin (CS / PL) composite fibers prepared by the present invention have excellent anti-swelling properties, mechanical properties, flexibility and flame retardancy, which are significantly superior to commercially available artificial hair.

[0062] Specifically:

[0063] (1) Chitosan and punicalagin have good compatibility. When the concentration of NaOH in the coagulation bath is 3% and the addition amount of PL is 5.0% w / w, the breaking strength of the CS / PL composite fiber is increased the most, which is 50% higher than that of the CS fiber, and the elongation at break is hardly lost.

[0064] (2) Compared with the CS fiber dyed after spinning, the CS / PL composite fiber has a natural brownish-yellow color, and the K / S value can reach up to 17.53, which is increased by 250%; and it has high color fastness, and the color fastness to sunlight reaches level 5.

[0065] (3) The anti-swelling performance and water resistance stability of the CS / PL composite fiber are improved.

[0066] (4) The CS / PL composite fiber can be applied to the field of artificial hair, and its bending resistance, drapability, and suspension center height are significantly better than those of the existing commercially available artificial hair. Description of the Drawings

[0067] Figure 1 shows the rheological properties of CS / PL composite spinning solutions with different PL addition amounts;

[0068] Figure 2 shows the influence of the concentration of sodium hydroxide in the coagulation bath and the addition amount of PL on the tensile mechanical properties of CS / PL composite fibers; among them, a is under the condition of coagulation bath NaOH - 3%, and b is under the condition of coagulation bath NaOH - 5%;

[0069] Figure 3 shows the K / S values of CS fibers, CS / PL composite fibers, and dyed CS fibers with different coagulation bath alkali concentrations;

[0070] Figure 4 shows the SEM detection images of CS fibers and CS / PL composite fibers; among them, a and c are the cross-section and fracture surface of CS fibers, and b and d are the cross-section and fracture surface of CS / PL composite fibers;

[0071] Figure 5 shows the relationship curve between the swelling ratio and time of CS fibers and CS / PL composite fibers;

[0072] Figure 6 shows the optical microscope images of CS / PL composite fibers and commercially available artificial hair; among them, a is the CS / PL composite fiber, and b is the commercially available artificial hair;

[0073] Figure 7 shows the bending resistance test results of CS fibers, CS / PL composite fibers, and commercially available artificial hair;

[0074] Figure 8 shows the draping effects of CS / PL composite fibers and commercially available artificial hair; among them, a is the CS fiber, b is the CS / PL composite fiber, and c is the commercially available artificial hair;

[0075] Figure 9 The suspension heights of CS / PL composite fiber and commercially available artificial hair; where a is CS fiber, b is CS / PL composite fiber, and c is commercially available artificial hair.

[0076] Figure 10 The combustion results of CS / PL composite fiber (left) and commercially available artificial hair (right).

[0077] Figure 11 The tensile rheological properties of CS fiber, CS / PL, and CS / TP composite spinning solutions.

[0078] Figure 12 The flow conditions of CS / PL and CS / TP composite spinning solutions after being placed for 1 to 7 days.

[0079] Figure 13 The viscosity test results of CS / PL and CS / TP composite spinning solutions on the seventh day of being placed.

[0080] Figure 14 The physical diagram of CS / TP composite fiber.

[0081] Figure 15 The observation results of CS / TP composite fiber under an optical microscope.

[0082] Figure 16 The bending resistance properties of CS fiber, CS / PL composite fiber, and CS / TP composite fiber. Specific implementation manners

[0083] The following describes the preferred embodiments of the present invention. It should be understood that the embodiments are for better explaining the present invention and are not used to limit the present invention.

[0084] Raw materials used in the embodiments:

[0085] Chitosan (deacetylation degree ≥ 85%, viscosity 1150 mPa·s) was purchased from Qingdao Yunzhou Biotechnology Co., Ltd.

[0086] Punicalagin (content 40%) was purchased from Shaanxi Haochen Biotechnology Co., Ltd.

[0087] Acetic acid, ethanol (anhydrous ethanol), glycerol (analytical pure, purity ≥ 99%), sodium hydroxide (analytical pure, purity ≥ 96%), all were purchased from Sinopharm Chemical Reagent Co., Ltd.

[0088] CS fiber was purchased from Qingdao Jifa New Materials Co., Ltd.

[0089] The solvent of the sodium hydroxide solution is water.

[0090] The solvent of the glycerol solution is water.

[0091] Test method:

[0092] 1. Testing the rheological properties of the spinning solution

[0093] Use a tensile rheometer to test the tensile rheological properties of the spinning solution.

[0094] Place a small amount of the spinning solution on the lower flat plate of the instrument (initial gap 2 mm), separate the upper flat plate from the lower flat plate at a preset strain rate and raise it to a preset height. The laser beam monitors the change in the diameter of the midpoint of the filament in real time, and repeat the test at least three times.

[0095] 2. Testing the mechanical properties

[0096] Use an electronic single fiber strength tester to test the mechanical properties of the fiber.

[0097] The test conditions are a specimen length of 20 mm, a tensile speed of 20 mm / min, and each sample is tested 20 times.

[0098] 3. Testing the swelling properties

[0099] Immerse the fiber in a certain amount of deionized water at room temperature to cause swelling, take it out at regular intervals (0.5 min - 10 min), remove the residual moisture on the surface of the fiber, and record the mass of the fiber before and after swelling respectively.

[0100] The swelling property is represented by the swelling ratio R, and the calculation formula is as follows:

[0101]

[0102] In the formula: R is the swelling ratio, W s is the mass of the fiber after swelling, g; W o is the mass of the dried fiber, g. Each sample is tested three times.

[0103] 4. Testing the microscopic morphology

[0104] After sputtering the composite fiber with gold, use a scanning electron microscope to observe the microscopic morphology of the fiber cross-section and fracture surface, and the scanning voltage is 5 Kv.

[0105] 5. Characterization of color and color fastness to sunlight

[0106] Use a computer color matching instrument to analyze the color of the fiber. Select the CS fiber as the standard sample, the light source is D65 10 Deg, each sample is tested twice, and record the K / S value.

[0107] Cut an appropriate amount of fiber samples, evenly spread them on a cardboard of a specified size and fix both ends. Refer to the standard of GB / T 8427-2019 "Textiles - Tests for colour fastness - Colour fastness to artificial light: Xenon arc", and test the color fastness to sunlight of the composite fiber.

[0108] Example 1: Preparation method of chitosan / punicalagin composite fiber

[0109] 1. Preparation of chitosan / punicalagin composite fiber

[0110] A method for preparing chitosan / punicalagin composite fiber (CS / PL) includes the following steps:

[0111] (1) Chitosan is dissolved in 2% w / w acetic acid aqueous solution, stirred in a water bath at 40 °C for 4 h to dissolve, then punicalagin is added, stirred in a water bath at 40 °C for 2 h, and then ultrasonically treated at 20 kHz for 15 min to obtain CS / PL composite spinning solution;

[0112] Among them, the final concentration of chitosan is 2% w / w of the spinning solution, and the final concentration of punicalagin (PL) is 2.5 - 10% w / w of chitosan (i.e., 0.05 - 0.2% w / w of the spinning solution);

[0113] (2) The CS / PL composite spinning solution is injected into different coagulation baths (3% and 5% w / w sodium hydroxide solutions are respectively mixed with ethanol, and the mass ratio is 3:1) through a micro-injection pump at a flow rate of 0.5 mL / min through a 19G needle. After the solidified filament is drawn by two drafting rollers (draft ratio is 1.2), it is left standing in 1% w / w glycerol aqueous solution for 1 h and then dried to prepare CS / PL composite fiber.

[0114] 2. Detection of the properties of CS / PL composite spinning solution and CS / PL composite fiber

[0115] (1) Rheological properties of CS / PL composite spinning solution

[0116] Take the CS / PL composite spinning solution prepared with different dosages of punicalagin in 1, and detect its rheological properties. The results are as Figure 1 shown.

[0117] The longer the time required for fluid fracture, the greater the viscosity of the spinning solution. The results show that with the increase of the PL addition amount, the viscosity of the CS / PL composite fiber first increases and then decreases, and reaches the highest when the addition amount is 5.0% w / w (i.e., 0.1% w / w of the spinning solution). This is because the phenolic substances in punicalagin form a cross-linked structure with chitosan; however, with the continuous increase of the PL addition amount, the number of free polyphenol molecules increases, destroying the formed cross-linked structure and causing the viscosity to decrease.

[0118] (2) Mechanical properties of CS / PL composite fiber

[0119] Take the CS / PL composite fiber prepared in 1 and detect its tensile mechanical properties. The results are shown in Table 1 and Figure 2 shown.

[0120] The results show that the breaking strength of the CS / PL composite fiber first increases and then decreases. When the PL addition amount is 5.0% w / w, the breaking strength reaches the maximum;

[0121] The concentration of sodium hydroxide in the coagulation bath also has a great influence on the mechanical properties of the composite fiber. Tables 1 and Figure 2 show that the breaking strength of the composite fiber in the coagulation bath of NaOH-5% is increased by up to 27%, but the elongation at break decreases, the specific work of fracture decreases, and the handle is relatively hard. The breaking strength of the composite fiber in the coagulation bath of NaOH-3% is increased by up to 50%, and the elongation at break is hardly lost.

[0122] Taking all factors into consideration, when the concentration of sodium hydroxide in the coagulation bath is 3% and the PL addition amount is 5.0%, the tensile mechanical properties of the composite fiber are the best. And according to GB / T 23167-2019 "Artificial Colored Hair Springs and Braids for Hair Products", the breaking strength of a single hair needs to be ≥40 cN, and the CS / PL composite fiber meets the requirements.

[0123] Table 1 Influence of alkali concentration in the coagulation bath and PL addition amount on the tensile mechanical properties of CS / PL composite fiber

[0124]

[0125] 3. Color of CS / PL composite fiber

[0126] Using commercially available CS fiber dyeing as a control sample, the dyeing conditions are PL dosages of 5% and 10% (o.w.f), bath ratio of 1:30, dyeing temperature of 90 °C, heating rate of 3 °C / min, and heat preservation for 30 min to obtain commercially available dyed CS fiber.

[0127] Detect the influence of PL addition amount and alkali concentration in the coagulation bath on the dyeing effect. The results are shown in Table 2 and Figure 3 as follows.

[0128] Table 2 Influence of alkali concentration in the coagulation bath and PL addition amount on the color of CS / PL composite fiber

[0129]

[0130] The results show that with the increase of PL addition amount, the K / S value of the composite fiber increases and the color gradually becomes darker; the concentration of sodium hydroxide in the coagulation bath also affects the color of the composite fiber. When the PL addition amount is small (2.5%, 5.0%), the color of the composite fiber in the coagulation bath of NaOH-5% is darker; this is because punicalagin is a weak acid substance. Under alkaline conditions, the higher the concentration of OH - the more easily the phenolic hydroxyl group in punicalagin dissociates to generate free radicals, and the color will deepen.

[0131] However, as the addition amount of PL continues to increase, the color of the coagulation bath NaOH-5% composite fiber is lighter. This is because the excessive amount of punicalagin is unstable and extremely easy to enter the coagulation bath, resulting in a decrease in the color of the composite fiber.

[0132] Taking the dyed CS fiber as a control, the results show that when the dosage of PL is 5% (o.w.f.), the K / S value of the dyed fiber is 5.5; when the dosage increases to 10% (o.w.f.), the K / S value of the dyed fiber is 8.8, still lower than that of the CS / PL composite fiber. As can be seen from Table 2, the light fastness of the CS / PL composite fiber all reaches level 5. According to GB / T 23167-2019 "Artificial Colored Hair Springs and Braids for Hair Products", the light fastness needs to be ≥ level 3-4, and the CS / PL composite fiber all meets the requirements.

[0133] Combining the mechanical and color properties, when the concentration of NaOH in the coagulation bath is 3% and the addition amount of PL is 5.0% w / w (i.e., 0.1% w / w of the spinning solution), the conditions are optimal, and the prepared CS / PL composite fiber has better comprehensive effects. Subsequent analysis will be carried out based on this.

[0134] Example 2: Detection of the Structure and Swelling Properties of CS / PL Composite Fibers

[0135] Take the CS / PL composite fiber prepared under the optimal conditions in Example 1, and detect its morphology and swelling properties, with the CS fiber as a control.

[0136] (1) Morphology Analysis

[0137] The SEM images of CS fiber and CS / PL composite fiber are as Figure 4 shown. The cross-sectional morphology shows that the surface of the CS / PL composite fiber is smooth and flat, without obvious particle dispersion, indicating good compatibility between the two. The cross-section of the CS fiber is lamellar and uneven, and the cross-section of the CS / PL composite fiber has enhanced unevenness, with strong particle sense and fiber drawing effect, which also verifies the increase in its tensile fracture strength.

[0138] (2) Swelling Property Analysis

[0139] The curves of the swelling ratio and time relationship of CS fiber and CS / PL composite fiber are as Figure 5 shown. The results show that it generally shows a trend of increasing first and then tending to be stable. After soaking for ten minutes, the swelling ratios of CS fiber and CS / PL composite fiber are 3.29 and 2.34 respectively. It can be seen that the anti-swelling property of the CS / PL composite fiber is improved. This is because the amino group in chitosan combines with the phenolic hydroxyl group in punicalagin to form a hydrogen bond network structure, reducing the free hydrophilic amino and phenolic hydroxyl groups.

[0140] Example 3: Application of CS / PL Composite Fibers in the Preparation of Artificial Hair

[0141] Take the CS / PL composite fiber prepared under the optimal conditions in Example 1 (NaOH concentration is 3%, PL addition amount is 5.0% w / w), combine it to obtain artificial hair, use 0.7 ± 0.1 g of fiber artificial hair as the test sample, and use commercially available artificial hair and CS fiber as controls to detect the performance of artificial hair.

[0142] (1) Hair strand diameter

[0143] Use an optical microscope to observe the CS / PL composite fiber and commercially purchased artificial hair. The results are as Figure 6 shown. The results show that it can be found that the surface of the CS / PL composite fiber is smooth and flat, indicating good compatibility between chitosan and punicalagin. The diameter of the CS / PL composite fiber is close to that of artificial hair. At the same time, the linear density of the CS / PL composite fiber is calculated to be 97.24 dtex, and the linear density of artificial hair is 93.33 dtex, and the two linear densities are close.

[0144] (2) Bending resistance test

[0145] The XCB-1AN type fiber bending resistance tester can be used for the bending resistance test of industrial filaments and artificial hair fibers. The double-end clamping three-bending method is used to test the maximum bending resistance of the fiber to reflect the bending resistance ability of the fiber material and characterize the soft performance of the fiber material. The test conditions are as follows: the specimen clamping length is 10 mm, the rising speed of the lower chuck is 10 mm / min, and each sample is tested 20 times.

[0146] The results are as Figure 7 shown. The average maximum bending resistances of equal amounts of CS fiber, CS / PL composite fiber, and commercially available artificial hair fiber are 3.65, 3.56, and 3.87 respectively. Compared with artificial hair, after the CS / PL composite fiber reaches the maximum bending resistance, as the clamping distance continues to decrease, the bending resistance drops more, indicating that the CS / PL composite fiber is softer.

[0147] (3) Drape

[0148] For the CS fiber, CS / PL composite fiber, and commercially purchased artificial hair strands with both ends neat and equal in length, one end is held, and the other end hangs naturally and is combed.

[0149] The results are as Figure 8 shown. The results show that before combing, all three show a neat and natural drooping effect, but due to the use of synthetic fiber filaments, the commercially purchased artificial hair is prone to static electricity after combing, and the hair strands show obvious roughness.

[0150] (4) Suspension center height

[0151] The suspension center height of CS fiber, CS / PL composite fiber and commercially available artificial hair filaments was detected according to GB / T 43004-2023 "Test Method for the Softness of Hair Products". In the vertical plane, hold both ends of the fiber to bend it into a heart shape, and test its suspension center height, that is, the distance between the lowest point of the heart shape and the clamping point. The length of the tested fiber and hair filament is 35 ± 1 cm, and the weight is 0.7 ± 0.1 g.

[0152] The results are as Figure 9 shown. The results show that the suspension center height of CS fiber is 16.5 cm, the suspension center height of CS / PL composite fiber is 14.1 cm, and the suspension center height of commercially available artificial hair filaments is 11.3 cm. It can be seen that CS fiber is the softest, but considering the application scenarios of artificial hair, it cannot be too soft and flabby. Therefore, the suspension center height of CS / PL composite fiber is more appropriate.

[0153] (5) Flame retardant effect

[0154] Take CS / PL composite fiber and commercially available artificial hair filaments, the tested fiber and hair filament lengths are both 15 cm, and the weight is 0.2 g. Ignite them simultaneously and observe their combustion states.

[0155] The results are as Figure 10 shown. The results show that the CS / PL composite fiber can self-extinguish only 1 s after ignition, while the commercially available artificial hair continues to burn and has molten dripping. This is because chitosan has a high carbon element content, has side chain hydroxyl and amino groups, and can be carbonized and release non-toxic and non-combustible gases such as CO2, NH3 and N2 when heated and decomposed, having a certain flame retardant effect.

[0156] Comparative Example 1: Preparation of composite fiber using tea polyphenols

[0157] On the basis of Example 1, punicacortein was replaced with tea polyphenols, and the remaining steps were the same as those in Example 1.

[0158] The properties of chitosan / tea polyphenol composite fiber (CS / TP) were detected, and the results are as follows.

[0159] 1. Properties of spinning solution

[0160] (1) Rheological properties

[0161] The tensile rheological properties of the spinning solution are as Figure 11 shown. The results show that the viscosity of CS / TP composite spinning solution is significantly lower than that of CS / PL composite spinning solution, indicating that the crosslinking effect of chitosan and tea polyphenols is relatively poor.

[0162] During the preparation of CS / TP composite spinning solution, it was found that as the standing time of the spinning solution increased, the viscosity of the spinning solution decreased; 1 ml of spinning solution was taken separately in a petri dish every day to observe its state, and the flow conditions of the spinning solution on the 1st - 7th days are asFigure 12 As shown, it can be seen that the spreading area of the CS / TP composite spinning solution increases significantly over time.

[0163] (2) Viscosity of the spinning solution

[0164] The composite spinning solution was advanced at a constant speed using a propeller, and the viscosity of the spinning solution was measured. The results are as Figure 13 shown. The results indicate that after 7 days of storage, the viscosity of the CS / PL composite spinning solution is still relatively high, forming long fluid filaments, while the CS / TP composite spinning solution has already dripped in the form of water droplets.

[0165] This is because the macromolecular structure of punicalagin may have a stronger steric hindrance effect and more binding sites. Its conjugated cyclic structure may enhance the hydrophobic interaction or π-π stacking with chitosan, forming a more compact physical cross-linking network and resisting dissociation. While the tea polyphenol molecule is smaller and its structure is more flexible, and its hydrogen bond or electrostatic binding with chitosan is weak; at the same time, tea polyphenols are easily oxidized to quinone substances, resulting in a reduction of phenolic hydroxyl groups and weakening the hydrogen bond interaction with chitosan.

[0166] 2. Fiber properties

[0167] (1) CS / TP composite fiber

[0168] The CS / TP composite fiber is as Figure 14 shown, and the results of optical microscope observation are as Figure 15 shown. The results indicate that chitosan and tea polyphenols have good compatibility, and the linear density of the CS / TP composite fiber is 166.15 dtex.

[0169] (2) Bending resistance of the fiber

[0170] The bending resistances of CS fiber, CS / PL composite fiber, and CS / TP composite fiber are as Figure 16 shown. The results indicate that the average maximum bending forces of CS fiber and CS / TP composite fiber are 3.65 and 2.08 respectively. It is measured that the maximum bending forces of CS fiber and CS / PL composite fiber are close to those of commercially available artificial hair, while the maximum bending force of CS / TP composite fiber is significantly lower than that of CS fiber and CS / PL composite fiber.

[0171] Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person familiar with this technology can make various modifications and alterations without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be defined by the claims.

Claims

1. A method for preparing chitosan / punicalagin composite fibers, characterized in that, It includes the following steps: (1) Dissolve chitosan in an acetic acid aqueous solution, add punicalagin, and mix well to obtain a chitosan / punicalagin composite spinning solution; Among them, the final concentration of chitosan in the chitosan / punicalagin composite spinning solution is 1-3% w / w, and the final concentration of punicalagin is 0.05-0.2% w / w; (2) Perform wet spinning on the chitosan / punicalagin composite spinning solution and carry out coagulation in a coagulation bath to prepare chitosan / punicalagin composite fibers.

2. The method according to claim 1, wherein In step (2), the coagulation bath is obtained by mixing a sodium hydroxide solution and ethanol according to a mass ratio of 2-3:1; Optionally, the concentration of the sodium hydroxide solution is 3-5% w / w; Optionally, wet spinning is to inject the chitosan / punicalagin composite spinning solution into the coagulation bath through a needle at a flow rate of 0.4-0.6 mL / min. After being drawn by two drafting rollers, it is left standing and dried in glycerol to prepare chitosan / punicalagin composite fibers.

3. The method according to claim 1, characterized in that In step (1), the concentration of the acetic acid aqueous solution is 1-3% w / w; Optionally, in step (1), chitosan is dissolved in the acetic acid aqueous solution and stirred at 35-40 °C for 4-6 h.

4. The method according to claim 1, characterized in that, Mixing in step (1) is to stir at 35-40 °C for 2-3 h and then perform ultrasonic treatment at 15-20 kHz for 15-20 min.

5. Chitosan / punicalagin composite fibers prepared by the method according to any one of claims 1-4.

6. Application of the method according to any one of claims 1-4 or the chitosan / punicalagin composite fibers according to claim 5 in the field of functional textiles; Optionally, the application in the field of functional textiles includes the preparation of clothing, artificial hair, and medical textiles.

7. A product, characterized in that, The product contains the chitosan / punicalagin composite fibers according to claim 5; Optionally, the product includes artificial hair, medical textiles, and clothing.

8. An artificial hair, characterized in that, Artificial hair is prepared from chitosan / punicalagin composite fibers; Among them, the preparation method of the chitosan / punicalagin composite fibers includes the following steps: (1) Dissolve chitosan in an acetic acid aqueous solution, add punicalagin, and mix well to obtain a chitosan / punicalagin composite spinning solution; Among them, the final concentration of chitosan in the chitosan / punicalagin composite spinning solution is 1-3% w / w, and the final concentration of punicalagin is 0.05-0.2% w / w; (2) Perform wet spinning on the chitosan / punicalagin composite spinning solution and carry out coagulation in a coagulation bath to prepare chitosan / punicalagin composite fibers.

9. A method for preparing artificial hair, characterized in that, Artificial hair is composed of chitosan / punicalagin composite fibers; Among them, the preparation method of the chitosan / punicalagin composite fibers includes the following steps: (1) Dissolve chitosan in an acetic acid aqueous solution, add punicalagin, and mix well to obtain a chitosan / punicalagin composite spinning solution; Among them, the final concentration of chitosan in the chitosan / punicalagin composite spinning solution is 1-3% w / w, and the final concentration of punicalagin is 0.05-0.2% w / w; (2) Perform wet spinning on the chitosan / punicalagin composite spinning solution and carry out coagulation in a coagulation bath to prepare chitosan / punicalagin composite fibers.

10. A method for simultaneously improving the mechanical properties, compliance properties, and flame retardancy of chitosan composite fibers, characterized in that, The method includes the following steps: (1) Dissolve chitosan in an aqueous acetic acid solution, add punicalagin, and mix well to obtain a chitosan / punicalagin composite spinning solution; Among them, the final concentration of chitosan in the chitosan / punicalagin composite spinning solution is 1-3% w / w, and the final concentration of punicalagin is 0.05-0.2% w / w; (2) Perform wet spinning on the chitosan / punicalagin composite spinning solution and carry out coagulation in a coagulation bath to prepare chitosan / punicalagin composite fibers.

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