Multifunctional composite washing-free headband and preparation method thereof

Abstract

The invention relates to a multifunctional composite washing-free headscarf and a preparation method thereof, and belongs to the technical field of textiles. The preparation method comprises the following steps: S1, dissolving modified mesoporous silicon spheres and a dispersing agent in water to obtain a modified silicon sphere suspension; dissolving silk protein in a guanidine hydrochloride aqueous solution to obtain a silk protein solution; performing swelling treatment on cellulose in a sodium hydroxide solution, adding a thickening agent, uniformly mixing, and performing freezing treatment to obtain a cellulose solution; s2, uniformly stirring the modified silicon ball suspension, the fibroin solution, the cellulose solution and a binder to obtain a composite spinning solution; s3, extruding the composite spinning solution into a coagulating bath, and washing and cross-linking to obtain composite fibers; s4, porous non-woven fabric is prepared from the composite fibers through a spunlace method, then the porous non-woven fabric is soaked in a functional additive solution, the composite washing-free headscarf is obtained through drying, and unification of durability, high efficiency and safety of the composite washing-free headscarf in oil absorption and control, hair quality repair and hair follicle activation performance is achieved.

Description

Technical Field

[0001] This invention belongs to the field of textile technology, and in particular relates to a multifunctional composite washable headscarf and its preparation method. Background Technology

[0002] With the ever-accelerating pace of modern life and the increasing emphasis on personal care, leave-in care products have gradually become an important development trend in the daily chemical industry due to their convenience, efficiency, and wide applicability. Among these, leave-in headscarves, as a representative product, integrate multiple functions such as scalp cleansing, oil absorption, nutrient replenishment, and hair repair. They are particularly suitable for the daily needs of people with fast-paced lifestyles, while also meeting the special usage scenarios of travel, post-operative care, or environments with limited water resources, demonstrating significant practical value.

[0003] Compared to traditional water-based hair care methods, no-rinse headscarves not only effectively save water resources and reduce time costs, but also avoid problems such as weakened scalp barrier function and damage to hair cuticle caused by frequent washing. Therefore, they have formed a stable demand among some consumer groups, and the industry is gradually moving towards multi-functionality, compositeness and material innovation, with considerable market potential.

[0004] However, currently available no-wash headscarves still generally face several technical bottlenecks: First, the base materials are mostly conventional polyester, viscose, or non-woven fabrics. These materials have relatively simple structures, uneven pore distribution, and limited specific surface area, directly resulting in low oil absorption capacity and insufficient oil-locking ability. Secondary pollution is likely to occur during use, affecting the user experience. Second, functional ingredients such as vitamins, plant extracts, and protein-based active substances are usually only attached to the fiber surface through impregnation or spraying. This results in problems such as low loading capacity, excessively fast release rate, and weak binding force with fibers. They are prone to loss or inactivation during repeated use or storage, making it difficult to achieve the goal of long-term repair and stable efficacy. Third, some products introduce chemical modification or polymer coating processes to enhance a specific function. However, this approach often leads to side effects such as fabric stiffness, reduced breathability, and increased skin irritation, further restricting the improvement of product quality.

[0005] Therefore, developing a no-wash head towel that combines high adsorption capacity, structural stability, and good biocompatibility has become an urgent task to promote technological upgrading in the no-wash head towel field and meet higher market demands. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a multifunctional composite no-wash head towel and its preparation method. Through the synergistic effects of "bifunctional modification of mesoporous silica and mesoporous organosilicon", "silk protein molecular chain regulation", and "genipin-specific bio-crosslinking", the multifunctional composite no-wash head towel achieves a long-lasting, efficient, and safe balance in terms of oil absorption and control, hair repair, and hair follicle activation.

[0007] The first objective of this invention is to provide a method for preparing a multifunctional composite washable headscarf, comprising the following steps: S1. Modified mesoporous silica spheres and a dispersant are dissolved in water and subjected to ultrasonic treatment to obtain a modified silica sphere suspension; the modified mesoporous silica spheres are silane coupling agent modified mesoporous silica spheres; the mesoporous silica spheres include mesoporous silica and mesoporous organosilicon; the mesoporous organosilicon is selected from one or more of ethyl bridging organosilicon, phenyl bridging organosilicon, azide bridging organosilicon and amino acid bridging organosilicon; the silane coupling agent is obtained by compounding KH-550 and KH-570 in a mass ratio of (2-4):1; Silk fibroin was dissolved in an aqueous solution of guanidine hydrochloride, and purified by dialysis to obtain a silk fibroin solution. Cellulose is swollen in sodium hydroxide solution, then a thickener is added and mixed evenly, followed by freezing to obtain a cellulose solution; S2. Mix the modified silica ball suspension and silk protein solution described in S1 and stir magnetically until uniform. Then, add cellulose solution and binder and stir evenly with shearing to obtain composite spinning solution. S3. The composite spinning solution described in S2 is extruded into a coagulation bath by wet spinning. After the fiber is formed, it is washed, soaked in genipin solution for cross-linking reaction, and then vacuum dried to obtain composite fiber. S4. The composite fibers described in S3 are made into porous nonwoven fabric by hydroentangling, and then soaked in a functional additive solution and dried to obtain the multifunctional composite wash-free headscarf.

[0008] In one embodiment of the present invention, in S1, the dispersant is selected from one or more of polyethylene glycol, polyvinylpyrrolidone, sodium dodecyl sulfate, Tween-80 and Span-60; The mass ratio of mesoporous silica to mesoporous organosilicon is 1:(2-4). The mesoporous silica and mesoporous organosilicon have independently 100nm-200nm particle sizes and independently 2nm-50nm pore sizes. The modified silica ball suspension contains 9%-13% by mass of modified mesoporous silica balls and 0.08%-0.12% by mass of dispersant.

[0009] In one embodiment of the present invention, in S1, the concentration of the guanidine hydrochloride aqueous solution is 6.8 mol / L-7.2 mol / L; The silk fibroin solution contains 6%-8% silk fibroin by mass, has a molecular weight of 2kDa-80kDa, and a viscosity of 300mPa·s-500mPa·s.

[0010] In one embodiment of the present invention, in S1, the mass fraction of the sodium hydroxide solution is 7%-9%; The swelling treatment is performed at a temperature of 48℃-52℃ for a time of 1.5h-3h. The thickener is selected from one or more of urea, polyvinylpyrrolidone, sodium lauryl sulfate, Tween-80, and Span-60; The freezing treatment is performed at a temperature of -6°C to -4°C for a time of 0.5h to 1.5h. The cellulose solution contains 5%-7% cellulose by mass, has a degree of polymerization of 500-800, contains 2.8%-3.2% thickener by mass, and has a viscosity of 800 mPa·s-1000 mPa·s.

[0011] In one embodiment of the present invention, in S2, the mass ratio of the modified silica ball suspension, silk fibroin solution, and cellulose solution is (1.3-1.7):1:(5.6-6.0). The binder is selected from one or more of polyvinyl alcohol, polyacrylic acid, sodium alginate, sodium carboxymethyl cellulose and polyurethane; preferably, the binder is polyvinyl alcohol, whose hydroxyl groups on its molecular chain can form hydrogen bonds with cellulose, silk protein and modified mesoporous silica spheres, and can be separated in the coagulation bath by salting out, thereby achieving physical entanglement and anchoring of each component. The magnetic stirring was performed at 28℃-32℃ and 280rpm-320rpm for 28min-32min. The shearing and stirring were performed at 38℃-42℃ and 780rpm-820rpm for 55min-65min. The mass fraction of binder in the composite spinning solution is 1.8%-2.2%.

[0012] In one embodiment of the present invention, in S3, the process parameters of the wet spinning are: the orifice diameter of the spinneret is 0.14mm-0.16mm, the aspect ratio is (4.8-5.2):1, and the spinning speed is 5m / min-8m / min; The coagulation bath contains 11%-13% ammonium sulfate and 4.5%-5.5% ethanol. When the composite spinning solution is extruded into the coagulation bath, cellulose rapidly coagulates to form a fiber skeleton, while silk fibroin dehydrates, entangles, and forms hydrogen bonds with cellulose. Mesoporous silica spheres can also form chemical bonds (amide bonds, siloxane bonds) and hydrogen bonds with cellulose and silk fibroin through surface-modified groups. This is because the amino groups provided by the silane coupling agent can form amide bonds with the carboxyl groups of silk fibroin under suitable conditions, and can also form siloxane bonds with the hydroxyl groups of silica spheres and cellulose / silk fibroin. The coagulation bath is not only a physical coagulation site, but also a "reaction field" where multiple chemical and physical interactions (chemical bond formation, hydrogen bond enhancement, salting-out induced phase separation, chain entanglement) occur simultaneously, which makes the final fiber structure more stable.

[0013] In one embodiment of the present invention, in step S3, the mass fraction of the genipin solution is 0.5%-1.5%; The cross-linking reaction is carried out at a temperature of 35℃-40℃ for 2h-5h.

[0014] In one embodiment of the present invention, in S4, the hydroentangling process is carried out at 25℃-30℃, firstly by pre-hydroentangling at 10MPa-15MPa 2-4 times to make the fibers initially entangled, then by main hydroentangling at 18MPa-22MPa 4-6 times to make the fibers form a stable structure, and finally by post-hydroentangling at 8MPa-10MPa 1-3 times to finish the fabric surface.

[0015] In one embodiment of the present invention, in S4, the soaking temperature is 35°C-45°C and the soaking time is 15 min-25 min; The functional additive solution contains panthenol at a mass fraction of 0.5%-1%, vitamin E at a mass fraction of 0.3%-0.8%, and polysorbate-80 at a mass fraction of 0.2%-0.5%.

[0016] The second objective of this invention is to provide a multifunctional composite wash-free headscarf prepared by the method described above.

[0017] The technical solution of the present invention has the following advantages compared with the prior art: (1) The preparation method described in this invention uses a bifunctional modification treatment of mesoporous silica balls by combining KH-550 and KH-570. This modification can not only improve the surface grafting rate of silica balls, but also make silica balls form a stable suspension with uniform particle size and uniform dispersion. First, the amino group (-NH2) introduced by KH-550 can provide a covalent anchoring point for genipin crosslinking. Second, the double bond (C=C) introduced by KH-570 can enhance the compatibility of mesoporous silica balls in organic phases (such as silk fibroin matrix). At the same time, mesoporous silica balls can form strong chemical bonds with cellulose and silk fibroin through amino groups and double bonds, respectively, which significantly improves the loading stability and wash resistance of functional components. Moreover, during the crosslinking process of genipin, the amino groups on the surface of the modified mesoporous silica spheres actively participate in the reaction and are covalently integrated into the three-dimensional network together with silk protein and cellulose, realizing a fundamental transformation from "physical filling" to "chemical anchoring". This firm anchoring not only changes the load stability of the silica spheres in the fiber, but also ensures the long-term effectiveness of its porous structure.

[0018] (2) The preparation method described in this invention first precisely controls the molecular weight of silk protein to 2kDa-80kDa, and then uses different pore sizes of mesoporous silica spheres to achieve graded loading, thereby constructing an intelligent release system; wherein, small molecule oligopeptides (<2kDa) can be adsorbed in pores of 2nm-5nm for deep penetration and repair of hair, medium molecular weight polypeptides (2kDa-10kDa) are loaded in mesopores of 5nm-15nm to achieve continuous nourishment and filling of the middle layer of hair, and large molecule proteins (10kDa-80kDa) are cross-linked with genipin and anchored to the pore openings and fiber network of macropores of 15nm-50nm to form a durable surface protective film. This multi-level loading and controlled release mechanism with "pore size-molecular weight" matching allows the headscarf to achieve both immediate repair and long-lasting nourishment. Furthermore, through the aforementioned technologies of controlling the molecular weight of silk protein, graded loading of mesoporous silica spheres, and controlled release, the headscarf is ensured to have multi-scale repair functions. Ultimately, this enables the no-wash headscarf to achieve integrated and efficient care from surface protection to deep repair, meeting multiple needs for hair and scalp health.

[0019] (3) The preparation method described in this invention constructs a stable structure with both excellent mechanical properties and biological activity through a synergistic process of wet spinning and genipin crosslinking. In the coagulation bath stage of wet spinning, cellulose rapidly forms a macroscopic skeleton, while silk fibroin is simultaneously dehydrated, entangled, and forms hydrogen bonds. Subsequently, genipin acts as a "molecular bridge," and its active groups undergo specific covalent crosslinking with the amino groups of silk fibroin, the hydroxyl groups of cellulose, and the amino groups on the surface of modified silica spheres. The interfacial bonding is further strengthened through aldehyde crosslinking, ultimately forming a "three-in-one" homogeneous network. Furthermore, by controlling the degree of crosslinking, the structural strength and material flexibility can be balanced. At the same time, this covalent network can effectively resist mechanical and chemical erosion caused by water washing, thus optimizing durability. Furthermore, this invention also prepares a three-dimensional porous nonwoven fabric through a gradient pressure hydroentangling process, and further optimizes the overall structural stability by combining genipin crosslinking with multiphase chemical bonding of silica spheres, proteins, and cellulose. This significantly improves the adsorption capacity, structural stability, and component retention capacity of the nonwoven fabric, enabling it to load and lock in more functional components within the same area, thereby improving care efficiency and extending product lifespan. In terms of safety and functionality, the natural properties of genipin ensure extremely high biosafety, with a cytotoxicity test RGR>98%. Moreover, the crosslinking product of genipin and silk protein also exhibits the potential to activate hair follicle cells, enhancing their activity.

[0020] (4) The preparation method described in this invention uses a functionalized finishing process to load functional additives such as panthenol and vitamin E onto the surface of porous nonwoven fabric. With the help of the graded controlled release characteristics of mesoporous silica balls, it achieves efficient repair and hair follicle activation. At the same time, the product has the characteristic of self-loading functional ingredients and can be directly applied to hair and scalp without additional pretreatment. It is suitable for various scenarios such as fast-paced life, travel, and underwater environment, and finally provides an efficient and long-lasting solution for no-rinse hair care products. Detailed Implementation

[0021] The present invention will be further described below with reference to specific embodiments, so that those skilled in the art can better understand and implement the present invention, but the embodiments are not intended to limit the present invention.

[0022] In this invention, unless otherwise stated, the mesoporous silica used in the embodiments of this invention is purchased from Jiangsu Argon Krypton Xenon Materials Technology Co., Ltd., model number 643645-5G, with a particle size of approximately 150 nm and a pore size of approximately 2 nm-50 nm; the mesoporous organosilicon is alkyl-bridged organosilicon, purchased from Shanghai Tewei Fuxin Materials Technology Co., Ltd., model number THS-CH-50, with a particle size of approximately 100 nm and a pore size of approximately 2 nm-50 nm.

[0023] In this invention, unless otherwise stated, the polyvinyl alcohol used in the embodiments of this invention was purchased from Shanghai Titan Technology Co., Ltd., with product number 88954D, degree of polymerization of 1700-1800 and degree of alcoholysis of 87%-89%.

[0024] Example 1

[0025] The multifunctional composite wash-free headscarf and its preparation method in this embodiment specifically include the following steps: S1. Preparation of modified mesoporous silica spheres: Preparation of modified mesoporous silica: 3.75 g of mesoporous silica was dispersed in 75 mL of ethanol / water solution (volume ratio 3:1), and 0.19 g of silane coupling agent (mass ratio of KH-550 and KH-570 3:1) was added. The mixture was magnetically stirred at 65 °C and 300 rpm for 3 h. After centrifugation and washing three times, the mixture was dried in a vacuum oven at 80 °C for 6 h to obtain modified mesoporous silica. Preparation of modified mesoporous organosilicon: 11.25 g of mesoporous organosilicon was dispersed in 225 mL of ethanol / water solution (volume ratio 4:1), and 0.56 g of silane coupling agent (mass ratio of KH-550 and KH-570 3:1) was added. The mixture was magnetically stirred at 55 °C and 300 rpm for 4 h. After centrifugation and washing three times, the mixture was dried in a vacuum oven at 80 °C for 6 h to obtain modified mesoporous organosilicon. S2, Preparation of precursor solution Mesoporous organosilicon and mesoporous silica were dissolved in water at a mass ratio of 3:1, and ultrasonically treated with 300W power for 12 minutes. Polyethylene glycol-400 was added and stirred evenly to obtain a modified silica ball suspension with a mass fraction of 11% and a mass fraction of 0.1% of polyethylene glycol-400. Silk fibroin was dissolved in a 7 mol / L guanidine hydrochloride aqueous solution and stirred in a 50°C water bath until completely dissolved (controlling the molecular weight of silk fibroin to be approximately 65,000 Da). The solution was then placed in a dialysis bag and dialyzed in deionized water for 48 hours (with the dialysate changed every 8 hours). After dialysis, the solution was concentrated to obtain a silk fibroin solution with a silk protein mass fraction of 7% and a viscosity of approximately 400 mPa·s. Cellulose with a degree of polymerization of 600 was added to a sodium hydroxide solution with a mass fraction of 8% and swollen at 50°C for 2 hours. Then, urea was added and stirred until completely dissolved. The solution was then frozen at -5°C for 1 hour to obtain a cellulose solution with a mass fraction of 6% cellulose, a mass fraction of 3% urea, and a viscosity of approximately 900 mPa·s. S3. Preparation of composite spinning solution The modified silica ball suspension and silk fibroin solution were mixed and magnetically stirred at 30°C and 300 rpm for 30 min. Then, cellulose solution and polyvinyl alcohol were added and sheared and stirred at 40°C and 800 rpm for 60 min to obtain a composite spinning solution with a polyvinyl alcohol mass fraction of 2%. The mass ratio of the modified silica ball suspension, silk fibroin solution and cellulose solution was 1.5:1:5.8. S4. Preparation of composite fibers The composite spinning solution was injected into a wet spinning device and extruded through a spinneret with an aperture of 0.15 mm and an aspect ratio of 5:1 at a spinning speed of 6 m / min into a coagulation bath (containing 12% ammonium sulfate and 5% ethanol by mass). After the fiber was formed, it was washed three times with deionized water at 40°C until the conductivity of the washing solution was ≤10 μS / cm. Then, the fiber was immersed in a genipin solution with a pH of 8.5 and a mass fraction of 1% and subjected to a crosslinking reaction at 40°C for 3.5 h. After the degree of crosslinking reached 25%, the fiber was placed in a vacuum oven and heated from room temperature to 60°C at a rate of 2°C / min. It was then dried under a vacuum of -0.08 MPa for 2 h, and the final moisture content of the fiber was controlled to be 9%, thus obtaining the composite fiber. S5. Preparation of nonwoven fabrics Composite fibers were processed into porous nonwoven fabric using a hydroentangling process. At 28°C, the fibers were first pre-hydroentangled three times at 12 MPa to induce initial entanglement; then, they were primarily hydroentangled five times at 20 MPa to form a stable network structure; finally, the fabric surface was finished with two final hydroentanglements at 9 MPa, resulting in a fabric weight of 65 g / m². 2 A nonwoven fabric with a porosity of 68% and a three-dimensional porous structure; S6. Preparation of Multifunctional Composite Wash-Free Headscarf The nonwoven fabric was immersed in a functional additive solution at 40℃ for 20 minutes, then dried at 52℃ to obtain an adsorption capacity of 0.9 g / m³. 2 A multifunctional composite no-wash headscarf; wherein, the functional additive solution contains panthenol at a mass fraction of 0.8%, vitamin E at a mass fraction of 0.5%, polysorbate-80 at a mass fraction of 0.35%, and the remainder is water.

[0026] Example 2

[0027] The process is basically the same as in Example 1, except that the mass ratio of mesoporous organosilicon to mesoporous silica is 4:1.

[0028] Example 3

[0029] The process is basically the same as in Example 1, except that the mass ratio of mesoporous organosilicon to mesoporous silica is 2:1.

[0030] Example 4

[0031] The process is basically the same as in Example 1, except that the mass ratio of KH-550 to KH-570 is 4:1.

[0032] Example 5

[0033] The process is basically the same as in Example 1, except that the mass ratio of KH-550 to KH-570 is 2:1.

[0034] Example 6

[0035] The basic structure is the same as in Example 1, except that the mass ratio of the modified silica ball suspension, silk fibroin solution and cellulose solution is 1.7:1.

[0036] Example 7

[0037] The process is basically the same as in Example 1, except that the mass ratio of the modified silica ball suspension, silk fibroin solution, and cellulose solution is 1.3:1.

[0038] Comparative Example 1

[0039] The process is basically the same as in Example 1, except that the nonwoven fabric is a commercially available nonwoven fabric (purchased from Kao Corporation of Japan, model number 14901301406092).

[0040] Comparative Example 2

[0041] The basic structure is the same as in Example 1, except that the modified mesoporous silica is replaced with modified mesoporous organosilicon.

[0042] Comparative Example 3

[0043] The basic structure is the same as in Example 1, except that the modified mesoporous organosilicon is replaced with modified mesoporous silica.

[0044] Comparative Example 4

[0045] The method is basically the same as in Example 1, except that the mass fraction of the genipin solution is adjusted to 2.5%.

[0046] Comparative Example 5

[0047] The basic principle is the same as in Example 1, except that the mesoporous silica and mesoporous organosilicon are not modified.

[0048] Comparative Example 6

[0049] The method is basically the same as in Example 1, except that the genipin solution is replaced with glutaraldehyde solution.

[0050] Test Example 1

[0051] The oil absorption, repair effect, hair follicle cell activity, washability, and silica ball retention rate of the no-wash headscarves prepared in Examples 1-7 and Comparative Examples 1-6 were tested. (1) Oil absorption: determined according to the standard GB / T 31119-2014 "Test Method for Oil Absorption of Textiles"; (2) Repair rate: The sample preparation was to select a standardized damaged human hair bundle (length 10cm, weight 0.50g) with a hair cuticle breakage rate ≥50% after bleaching and perming treatment. The treatment method was to place 1.0g of sample in 10.0mL of deionized water, shake and extract at 40℃ for 1h to obtain the extract, then completely immerse the hair bundle in the extract, stand at 32℃ for 24h, take it out and gently rinse with deionized water and air dry at room temperature. Evaluation method: The surface morphology of the hair bundle before and after treatment was observed by scanning electron microscope (SEM), and multiple fields of view were randomly selected to count the proportion of areas with intact and smooth hair cuticles, and then the repair rate was calculated.

[0052] (3) Hair follicle cell viability: Cell culture was performed using human scalp hair follicle dermal papillary cells (HFDPCs) in DMEM medium containing 10% fetal bovine serum at 37°C in a 5% CO2 incubator; sample processing involved immersing the sample in the medium at a ratio of 1 cm² / mL, extracting at 37°C for 24 h, and then filtering the extract through a 0.22 μm filter membrane. The cells were then cultured at 1×10⁻⁶ cells / mL. 4 Cells were seeded at a density of 1 / well in 96-well plates and cultured for 24 h. The medium was then replaced with fresh medium containing 50% extract. For assay, after another 24 h of culture, 20 μL of MTT solution (5 mg / mL) was added to each well, and the plates were incubated for 4 h. The supernatant was discarded, and 150 μL of DMSO was added. The plates were shaken for 10 min to dissolve the crystals, and the absorbance (OD value) of each well was measured at 490 nm using a microplate reader. The calculation formulas were: relative cell viability (%) = (OD experimental group / OD blank control group) × 100%, and activity enhancement rate (%) = relative cell viability - 100%. (4) Coefficient of friction: Refer to GB / T 29865 "Test Methods for Tactile Sensitivity of Textiles"; (5) Silicon ball retention rate: Scanning electron microscopy (SEM) combined with energy dispersive X-ray spectroscopy (EDS) was used to analyze the surface state of the sample before and after water washing. The silicon ball retention rate was estimated by analyzing the change in the weight percentage of silicon (Si) element. The calculation formula is: Silicon ball retention rate (%) = (Weight percentage of Si element in the sample after water washing / Weight percentage of Si element in the sample before water washing) × 100%; (6) Washing: The test was conducted in accordance with GB / T 12490-2014 "Textiles - Tests for color fastness to household and commercial washing". Table 1 shows the final measured performance of the no-wash headscarf, where "washable" refers to 5 washes: Table 1

[0053] As shown in Table 1, the no-wash headscarf of this embodiment combines oil absorption and control, hair repair, and hair follicle activation functions. Specifically, it absorbs more than 43% of its own weight in oil, achieves a 24-hour repair rate of over 71% for damaged hair, and increases scalp hair follicle cell activity by 16%-20%. It also effectively overcomes the problem of poor washability; after five washes, the silicone ball retention rate still exceeds 90%, and the repair function retention rate exceeds 80%. It is widely applicable to various scenarios such as fast-paced lifestyles, travel, and post-operative care. These properties are attributed to the synergistic effect of its "mesoporous silicone ball bifunctional modification—silk protein graded loading—genipin biocrosslinking," specifically including the "chemical anchoring + intelligent" of the silicone balls. The stable porous structure is formed by the "release" mechanism, the efficient bio-crosslinking of genipin, and the hydroentangling process. Among them, the mesoporous silica and organosilicon bicomponent silica spheres modified by KH-550 / KH-570 can achieve chemical anchoring with cellulose and silk protein through surface amino groups and double bonds. They can also achieve graded loading and controllable release of silk protein according to molecular weight through multi-level pore structure, allowing small molecule peptides to quickly penetrate and repair, and large molecule proteins to form a film for a long time. Genipin, as a natural crosslinking agent, can simultaneously construct a three-in-one covalent network of "cellulose-silicone protein-silica spheres" in the wet spinning coagulation bath, which not only endows the fiber with a flexible structure and high specific surface area, but also significantly improves its washability.

[0054] Comparing Example 1 and Comparative Example 1, it can be seen that when using ordinary commercially available nonwoven fabric, the oil absorption of the no-wash towel is only 16%, the repair rate is 20%, there is no effect on improving hair follicle cell activity, and no washability is demonstrated. This is because Comparative Example 1 uses a traditional physical impregnation process, where the functional components are only mechanically attached to the surface of the conventional nonwoven fabric without a strong bond or intelligent carrier support, making them easy to fall off and with limited adsorption and loading capacity. In contrast, Example 1 uses modified mesoporous silica spheres for chemical anchoring and genipin biocrosslinking, fixing the functional components in a three-dimensional porous structure. The mesoporous silica spheres also provide multi-level adsorption and controlled release channels, significantly improving performance and washability.

[0055] Comparing Example 1 and Comparative Example 2, it can be seen that when only modified mesoporous organosilicon is used, the oil absorption of the no-wash headscarf is 35%, the repair rate is 60%, the hair follicle cell survival rate is increased by 10%, the repair rate is maintained at 50% after washing, and the silica ball retention rate is 70%. This is because in Example 1, mesoporous silica and organosilicon are combined. The former provides a rigid framework and abundant micropores to enhance the adsorption load, while the latter improves organic compatibility. In Comparative Example 2, only organosilicon is used, which lacks the rigid support and high adsorption micropores of silica, resulting in a decrease in oil absorption load efficiency and insufficient fiber structure stability. During washing, the silica balls and functional components are easily lost.

[0056] Comparing Example 1 and Comparative Example 3, it can be seen that using only modified mesoporous silica resulted in a 33% oil absorption rate, a 58% repair rate, and only an 8% increase in hair follicle cell survival rate for the no-wash headscarf, with a silica ball retention rate of 65%. This is because mesoporous silica is highly hydrophilic and has poor compatibility with the organic phase of silk protein. In Comparative Example 3, it easily aggregates and blocks the adsorption channels, and its binding force with fibers is weak. In Example 1, organosilicon improved the affinity between silica balls and the organic matrix, promoted uniform dispersion, and enhanced the adsorption and binding effects.

[0057] Comparing Example 1 and Comparative Example 4, it can be seen that when the mass fraction of the genipin solution is too high, the oil absorption of the no-wash headscarf is 20%, the repair rate is 40%, the hair follicle cell survival rate increases by 5%, the friction coefficient is 0.35, the repair rate retention rate is 0% after washing, and the silicone ball retention rate is 15%. This is because the genipin concentration in Example 1 is appropriate, with a cross-linking degree of about 25%, forming a stable and flexible covalent network; while the genipin concentration in Comparative Example 4 is too high, leading to excessive cross-linking, brittle fiber network, pore collapse, inability to adsorb loaded functional ingredients, poor hand feel, and structural damage during washing resulting in a large loss of ingredients.

[0058] Comparing Example 1 and Comparative Example 5, it can be seen that without modification of mesoporous silica and mesoporous organosilicon, the oil absorption of the no-wash headscarf is 25%, the repair rate is 48%, the repair rate retention rate after washing is 66%, and the silica ball retention rate is 83%. This is because the silane coupling agent (KH-550 and KH-570 compound) in Example 1 can endow the silica balls with amino groups and double bonds, enabling them to form chemical bonds (amide bonds and siloxane bonds) with cellulose and silk protein to achieve chemical anchoring, and also improve the dispersibility of silica balls in the organic phase. The unmodified silica balls in Comparative Example 5 do not have these functional groups and exist in the fiber by physical filling. They are prone to agglomeration and blockage of adsorption channels, and the binding force with the fiber is weak, resulting in a decrease in oil absorption and repair performance. During washing, the silica balls and functional components are more easily lost, and the wash resistance is worse.

[0059] Comparing Example 1 and Comparative Example 6, it can be seen that when glutaraldehyde is used for crosslinking, the survival rate of hair follicle cells in the no-wash headscarf is not improved, the oil absorption is 30%, the repair rate is 50%, the repair rate is 50% after washing, and the silicone ball retention rate is 80%. This is because genipin is a natural crosslinking agent that forms a non-toxic covalent network and can activate hair follicle cells; glutaraldehyde has residual toxicity, which will lead to no improvement in cell activity, and it is also easy to deactivate functional components and damage fiber structure, resulting in performance and safety that are inferior to Example 1.

[0060] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for preparing a multifunctional composite washable headscarf, characterized in that, Includes the following steps: S1. Modified mesoporous silica spheres and a dispersant are dissolved in water and subjected to ultrasonic treatment to obtain a modified silica sphere suspension; the modified mesoporous silica spheres are silane coupling agent modified mesoporous silica spheres; the mesoporous silica spheres include mesoporous silica and mesoporous organosilicon; the mesoporous organosilicon is selected from one or more of ethyl bridging organosilicon, phenyl bridging organosilicon, azide bridging organosilicon and amino acid bridging organosilicon; the silane coupling agent is obtained by compounding KH-550 and KH-570 in a mass ratio of (2-4):1; Silk fibroin was dissolved in an aqueous solution of guanidine hydrochloride, and purified by dialysis to obtain a silk fibroin solution. Cellulose is swollen in sodium hydroxide solution, then a thickener is added and mixed evenly, followed by freezing to obtain a cellulose solution; S2. Mix the modified silica ball suspension and silk protein solution described in S1 and stir magnetically until uniform. Then, add cellulose solution and binder and stir evenly with shearing to obtain composite spinning solution. S3. The composite spinning solution described in S2 is extruded into a coagulation bath by wet spinning. After the fiber is formed, it is washed, soaked in genipin solution for cross-linking reaction, and then vacuum dried to obtain composite fiber. S4. The composite fibers described in S3 are made into porous nonwoven fabric by hydroentangling, and then soaked in a functional additive solution and dried to obtain the multifunctional composite wash-free headscarf.

2. The method for preparing the multifunctional composite washable headscarf according to claim 1, characterized in that, In S1, the dispersant is selected from one or more of polyethylene glycol, polyvinylpyrrolidone, sodium dodecyl sulfate, Tween-80, and Span-60; The mass ratio of mesoporous silica to mesoporous organosilicon is 1:(2-4). The mesoporous silica and mesoporous organosilicon have independently 100nm-200nm particle sizes and independently 2nm-50nm pore sizes. The modified silica ball suspension contains 9%-13% by mass of modified mesoporous silica balls and 0.08%-0.12% by mass of dispersant.

3. The method for preparing the multifunctional composite washable headscarf according to claim 1, characterized in that, In S1, the concentration of the guanidine hydrochloride aqueous solution is 6.8 mol / L-7.2 mol / L; The silk fibroin solution contains 6%-8% silk fibroin by mass, has a molecular weight of 2kDa-80kDa, and a viscosity of 300mPa·s-500mPa·s.

4. The method for preparing the multifunctional composite washable headscarf according to claim 1, characterized in that, In S1, the mass fraction of the sodium hydroxide solution is 7%-9%; The swelling treatment is performed at a temperature of 48℃-52℃ for a time of 1.5h-3h. The thickener is selected from one or more of urea, polyvinylpyrrolidone, sodium lauryl sulfate, Tween-80, and Span-60; The freezing treatment is performed at a temperature of -6°C to -4°C for a time of 0.5h to 1.5h. The cellulose solution contains 5%-7% cellulose by mass, has a degree of polymerization of 500-800, contains 2.8%-3.2% thickener by mass, and has a viscosity of 800 mPa·s-1000 mPa·s.

5. The method for preparing the multifunctional composite washable headscarf according to claim 1, characterized in that, In S2, the mass ratio of the modified silica ball suspension, silk fibroin solution, and cellulose solution is (1.3-1.7):1:(5.6-6.0). The adhesive is selected from one or more of polyvinyl alcohol, polyacrylic acid, sodium alginate, sodium carboxymethyl cellulose, and polyurethane; The magnetic stirring was performed at 28℃-32℃ and 280rpm-320rpm for 28min-32min. The shearing and stirring were performed at 38℃-42℃ and 780rpm-820rpm for 55min-65min. The mass fraction of binder in the composite spinning solution is 1.8%-2.2%.

6. The method for preparing the multifunctional composite washable headscarf according to claim 1, characterized in that, In S3, the process parameters for wet spinning are: the orifice diameter of the spinneret is 0.14mm-0.16mm, the aspect ratio is (4.8-5.2):1, and the spinning speed is 5m / min-8m / min; The ammonium sulfate added to the coagulation bath has a mass fraction of 11%-13%, and the ethanol has a mass fraction of 4.5%-5.5%.

7. The method for preparing the multifunctional composite washable headscarf according to claim 1, characterized in that, In S3, the mass fraction of the genipin solution is 0.5%-1.5%; The cross-linking reaction is carried out at a temperature of 35℃-40℃ for 2h-5h.

8. The method for preparing the multifunctional composite washable headscarf according to claim 1, characterized in that, In S4, the hydroentangling process is carried out at 25℃-30℃. First, the fibers are pre-hydroentangled 2-4 times at 10MPa-15MPa to initially entangle them. Then, the fibers are mainly hydroentangled 4-6 times at 18MPa-22MPa to form a stable structure. Finally, the fabric surface is finished by hydroentangling 1-3 times at 8MPa-10MPa.

9. The method for preparing the multifunctional composite washable headscarf according to claim 1, characterized in that, In S4, the soaking temperature is 35℃-45℃ and the soaking time is 15min-25min; The functional additive solution contains panthenol at a mass fraction of 0.5%-1%, vitamin E at a mass fraction of 0.3%-0.8%, and polysorbate-80 at a mass fraction of 0.2%-0.5%.

10. A multifunctional composite wash-free headscarf prepared by the method according to any one of claims 1-9.

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