Polypropylene fiber superfine denier composite long cilia top and preparation method thereof

Abstract

The invention relates to a polypropylene fiber superfine denier composite long cilia top and a preparation method thereof, and relates to the technical field of superfine denier fibers. The polypropylene fiber superfine denier composite long cilia strip comprises a long cilia strip body, a hydrophilic layer is arranged on the long cilia strip body, the hydrophilic layer is formed by curing a hydrophilic coating on the long cilia strip body, and a preparation method of the hydrophilic coating comprises the following steps: adding silk fibroin into deionized water, and stirring uniformly to obtain the hydrophilic coating. Fully stirring, adding tetraethoxysilane, uniformly stirring, and adding hydrochloric acid to adjust the pH value to 4, so as to obtain a hydrophilic coating; the method has the effect of improving the hydrophilicity of the long cilia tops.

Description

Technical Field

[0001] This application relates to the field of ultrafine denier fibers, and in particular to a polypropylene ultrafine denier composite long fiber sliver and its preparation method. Background Technology

[0002] Polypropylene (PP) ultrafine denier composite long fiber slivers, as a textile raw material, do indeed have significant advantages such as being lightweight, hydrophobic, having good warmth retention, and low cost, making them very suitable for use in filling, thermal insulation wadding, non-woven fabrics, and other fields.

[0003] When polypropylene (PP) microfiber composite long fiber strips are used as inner or outer layer fillings, they cannot absorb human sweat, which can easily cause a stuffy feeling and reduce the comfort of the user when wearing clothing made of PP microfiber composite long fiber strips. Summary of the Invention

[0004] To improve the hydrophilicity of polypropylene ultrafine denier composite long fiber slivers, this application provides a polypropylene ultrafine denier composite long fiber sliver and its preparation method.

[0005] In the first aspect, this application provides a polypropylene ultrafine denier composite long fiber sliver, which adopts the following technical solution: A polypropylene ultrafine denier composite long fiber sliver includes a long fiber sliver body, on which a hydrophilic layer is disposed. The hydrophilic layer is formed by curing a hydrophilic coating on the long fiber sliver body. The preparation method of the hydrophilic coating includes the following steps: Silk fibroin was added to deionized water and stirred thoroughly. Then, tetraethyl orthosilicate was added and stirred evenly. Hydrochloric acid was added to adjust the pH to 4 to obtain a hydrophilic coating.

[0006] By adopting the above technical solution, tetraethyl orthosilicate hydrolyzes under acidic conditions to generate silica particles. Silk fibroin contains hydrophilic amino and carboxyl groups. The silica particles form micropores on the surface of the long fiber sliver through physical adsorption, enhancing the capillary effect. Furthermore, the polar groups of silk fibroin and the silanol groups generated by tetraethyl orthosilicate form a hydrogen bond network, effectively improving the adhesion of the hydrophilic layer on the long fiber sliver and significantly improving the wetting efficiency.

[0007] Preferably, a silane coupling agent is added during the preparation of the hydrophilic coating, and the preparation method of the hydrophilic coating includes the following steps: A pre-hydrolyzed silane coupling agent solution was prepared by adding silane coupling agent to an ethanol-deionized water mixture. Silk fibroin was added to deionized water, stirred thoroughly, and then tetraethyl orthosilicate was added. After stirring evenly, the pre-hydrolyzed silane coupling agent solution was added, and stirring was continued. Hydrochloric acid was added to adjust the pH to 4 to obtain a hydrophilic coating.

[0008] By adopting the above technical solution, the amino groups on the silane coupling agent react with the carboxyl groups of silk fibroin, and the siloxane groups on the silane coupling agent condense with silica to form a "protein-coupling agent-silica" bridging structure, thereby covalently linking silk fibroin and silica, improving the stability of the hydrophilic layer in the body of the long fiber, and thus improving the hydrophilic durability of the long fiber.

[0009] Preferably, the mass ratio of silk fibroin, tetraethyl orthosilicate and silane coupling agent is 1:(1.1-1.3):0.03.

[0010] By adopting the above technical solution and controlling the mass ratio of silk fibroin, tetraethyl orthosilicate and silane coupling agent within the above range, the stability of the hydrophilic layer in the long fiber sliver body can be effectively improved.

[0011] Preferably, the silane coupling agent includes an aminosilane coupling agent.

[0012] Preferably, the silane coupling agent further includes a polyether-modified silane coupling agent.

[0013] By adopting the above technical solution, the flexibility of the polyether segments on the polyether-modified silane coupling agent offsets the rigidity of silica, while its hydrophilicity can improve the hydrophilicity of long fiber strands, thereby improving the formation of a "rigid bridging + flexible spacing" hybrid network by persiloxane condensation and enhancing stability.

[0014] Preferably, an antibacterial reinforcing layer is provided on the side of the hydrophilic layer away from the long fiber strand body. The antibacterial reinforcing layer is formed by curing an antibacterial reinforcing coating on the hydrophilic layer. The preparation method of the antibacterial reinforcing coating includes the following steps: adding dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride to a mixture of isopropanol and deionized water, stirring evenly, and then adding glacial acetic acid to adjust the pH to 5 to obtain the antibacterial reinforcing coating.

[0015] By adopting the above technical solution, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, due to the presence of a positively charged quaternary ammonium group, exhibits excellent bactericidal activity against negatively charged bacteria. Furthermore, due to the N-terminus of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride... + When exposed to the surface of long fiber strands, ionic conductivity is generated, thus giving the long fiber strands a good antistatic effect. Therefore, the long fiber strands are made hydrophilic by treatment with silk fibroin and tetraethyl orthosilicate, while dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride provides antibacterial properties. The combination of the two gives the long fiber strands moisture-wicking and antibacterial properties.

[0016] Furthermore, the unreacted amino groups (positively charged) of KH-550 can serve as adsorption sites for dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, enhancing the binding of quaternary ammonium salts through electrostatic attraction. Moreover, the dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride molecule contains silanoxy groups, which can undergo condensation reactions with hydroxyl groups on the surface of silk fibroin / silica to form Si-OC or Si-O-Si bonds, achieving chemical anchoring. This improves the stability of the antibacterial reinforcement layer on the hydrophilic layer, thereby enhancing the antibacterial stability of the long fiber strands.

[0017] Preferably, the modified preparation method of the dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride includes the following steps: Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added to anhydrous toluene and stirred until homogeneous. Polyethylene glycol was then added and stirred thoroughly. P-toluenesulfonic acid was then added to react with the mixture. After the reaction was completed, the mixture was distilled under reduced pressure, cooled, washed, and then distilled under reduced pressure again to obtain modified dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride.

[0018] By employing the above technical solution, polyethylene glycol segments are grafted onto dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride molecules. The hydrophilic segments of polyethylene glycol can improve the dispersibility of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride in the aqueous phase, reduce agglomeration, and effectively enhance the antibacterial effect of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride. At the same time, the hydroxyl groups of polyethylene glycol form hydrogen bonds with the amide bonds of silk fibroin, enhancing the stability of the antibacterial reinforcement layer.

[0019] Preferably, the mass ratio of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride to polyethylene glycol is 1:(0.52-0.62).

[0020] By adopting the above technical solution and controlling the mass ratio of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and polyethylene glycol within the above range, the antibacterial effect of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride can be effectively improved.

[0021] Preferably, the antibacterial reinforcing coating further includes polyethyleneimine, and the preparation method of the antibacterial reinforcing coating includes the following steps: Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added to a mixture of isopropanol and deionized water, stirred until homogeneous, and then polyethyleneimine was added and stirred thoroughly. Finally, glacial acetic acid was added to adjust the pH to 5 to obtain an antibacterial reinforced coating.

[0022] By adopting the above technical solution, polyethyleneimine is added to the antibacterial reinforcing coating. Its polyamino structure is electrostatically bonded to the carboxyl groups of silk fibroin. At the same time, the amino groups of polyethyleneimine react with the silanol groups generated by the hydrolysis of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, which enhances the interlayer crosslinking effect, reduces the shedding of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, and further improves the stability of the antibacterial layer on the hydrophilic layer.

[0023] Secondly, the method for preparing polypropylene ultrafine denier composite long fiber sliver as described in the first aspect of this application adopts the following technical solution: A method for preparing polypropylene ultrafine denier composite long fiber sliver includes the following steps: S1. The long fiber sliver body is immersed in a hydrophilic coating. After immersion, it is taken out and rolled, and then heat-treated to make the surface of the long fiber sliver body have a hydrophilic layer, thereby obtaining the primary composite long fiber sliver. S2. The primary composite long fiber sliver is immersed in the antibacterial reinforcing coating. After immersion, it is taken out and rolled, and then heat-treated to form an antibacterial reinforcing layer on the hydrophilic layer, thereby producing the composite long fiber sliver.

[0024] In summary, this application includes at least one of the following beneficial technical effects: 1. Tetraethyl orthosilicate hydrolyzes under acidic conditions to generate silica particles. Silk fibroin contains hydrophilic amino and carboxyl groups. The silica particles form micropores on the surface of the long fiber strand through physical adsorption, enhancing the capillary effect. Furthermore, the polar groups of silk fibroin and the silanol groups generated by tetraethyl orthosilicate form a hydrogen bond network, which effectively improves the adhesion of the hydrophilic layer on the long fiber strand and significantly improves the wetting efficiency.

[0025] 2. Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, due to the positively charged quaternary ammonium group, has a good bactericidal effect against negatively charged bacteria. Furthermore, due to the N-terminus of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride... + When exposed to the surface of long fiber strands, ionic conductivity is generated, giving the long fiber strands excellent antistatic properties. Therefore, treatment with silk fibroin and tetraethyl orthosilicate imparts hydrophilicity to the long fiber strands, while dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride provides antibacterial properties. The combination of these two components gives the long fiber strands both moisture-wicking and antibacterial properties. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the overall structure of a polypropylene ultrafine denier composite long fiber sliver in an embodiment of this application.

[0027] Explanation of reference numerals in the attached figures: 1. Long fiber strips; 2. Hydrophilic layer; 3. Antibacterial reinforcement layer. Detailed Implementation

[0028] The following is in conjunction with the appendix Figure 1 This application will be described in further detail.

[0029] This application discloses a polypropylene ultrafine denier composite long fiber sliver. (Refer to...) Figure 1 The polypropylene ultrafine denier composite long fiber sliver includes a long fiber sliver body 1, a hydrophilic layer 2 is provided on the long fiber sliver body 1, the hydrophilic layer 2 is formed by curing a hydrophilic coating on the long fiber sliver body 1; an antibacterial reinforcing layer 3 is provided on the side of the hydrophilic layer 2 away from the long fiber sliver body 1, the antibacterial reinforcing layer 3 is formed by curing an antibacterial reinforcing coating on the hydrophilic layer.

[0030] All raw materials involved in this application are commercially available. Among them, silk fibroin (CAS No.: 96690-41-4) is provided by Hubei Hongxin Ruiyu Fine Chemical Co., Ltd., tetraethyl orthosilicate (CAS No.: 78-10-4) is provided by Zhangjiagang Xinya Chemical Co., Ltd., dimethyl octadecyl [3-(trimethoxysilyl)propyl]ammonium chloride (CAS No.: 27668-52-6) is provided by Hubei Yongkuo Technology Co., Ltd., polyethylene glycol-600 (CAS No.: 25322-68-3) is provided by Shandong Qianfanshun Chemical Co., Ltd., polyethyleneimine (CAS No.: 9002-98-6) is provided by Shanghai Yihe Biotechnology Co., Ltd., and UM-ET10 is provided by Wuhan Anruike Materials Co., Ltd.

[0031] Example 1 The preparation method of hydrophilic coatings includes the following steps: 1g of silk fibroin was added to 60mL of deionized water and stirred at 600rpm for 1h at 40℃. Then 1.2g of tetraethyl orthosilicate was added and stirred at 400rpm for 2h at 25℃. Hydrochloric acid (1mol / L) was then added until the pH was 4 to obtain a hydrophilic coating.

[0032] The preparation method of polypropylene ultrafine denier composite long fiber sliver includes the following steps: The long fiber sliver body is immersed in a hydrophilic coating at 40°C with a roll weight of 70%. After 20 minutes, it is taken out and rolled, and then placed in a 120°C oven for drying for 5 minutes, so that a hydrophilic layer is formed on the surface of the long fiber sliver body, thus obtaining a composite long fiber sliver.

[0033] Example 2 The difference between Example 2 and Example 1 is that the hydrophilic coating also contains a silane coupling agent. The mass ratio of silk fibroin, tetraethyl orthosilicate, and silane coupling agent is 1:1.2:0.03. The silane coupling agent is an aminosilane coupling agent, and the aminosilane coupling agent is KH-550.

[0034] The preparation method of hydrophilic coatings includes the following steps: 0.03 g of silane coupling agent was added to 3 mL of ethanol-deionized water mixture (volume ratio of ethanol to deionized water was 1:3) to prepare a pre-hydrolyzed silane coupling agent solution. 1 g of silk fibroin was added to 60 mL of deionized water and stirred at 600 rpm for 1 h at 40 °C. Then 1.2 g of tetraethyl orthosilicate was added and stirred at 400 rpm for 2 h at 25 °C. The pre-hydrolyzed silane coupling agent solution was then added and stirred for 30 min. Finally, hydrochloric acid (1 mol / L) was added until the pH was 4 to prepare a hydrophilic coating.

[0035] Example 3 The difference between Example 3 and Example 2 is that the silane coupling agent includes an aminosilane coupling agent and a polyether-modified silane coupling agent. The aminosilane coupling agent is KH-550, and the polyether-modified silane coupling agent is UM-ET10. The mass ratio of KH-550 to UM-ET10 is 3:1.

[0036] The preparation method of silane coupling agents includes the following steps: KH-550 and UM-ET10 were mixed and stirred evenly to obtain a silane coupling agent.

[0037] Example 4 The preparation method of hydrophilic coatings includes the following steps: 0.03 g of silane coupling agent was added to 3 mL of ethanol-deionized water mixture (volume ratio of ethanol to deionized water was 1:3) to prepare a pre-hydrolyzed silane coupling agent solution. 1 g of silk fibroin was added to 60 mL of deionized water and stirred at 600 rpm for 1 h at 40 °C. Then 1.1 g of tetraethyl orthosilicate was added and stirred at 400 rpm for 2 h at 25 °C. The pre-hydrolyzed silane coupling agent solution was then added and stirred for 30 min. Finally, hydrochloric acid (1 mol / L) was added until the pH reached 4 to obtain a hydrophilic coating.

[0038] The silane coupling agents include aminosilane coupling agents and polyether-modified silane coupling agents. The aminosilane coupling agent is KH-550, and the polyether-modified silane coupling agent is UM-ET10. The mass ratio of KH-550 to UM-ET10 is 3:1.

[0039] The preparation method of silane coupling agents includes the following steps: KH-550 and UM-ET10 were mixed and stirred evenly to obtain an aminosilane coupling agent.

[0040] The preparation method of polypropylene ultrafine denier composite long fiber sliver includes the following steps: The long fiber sliver body is immersed in a hydrophilic coating at 40°C with a roll weight of 70%. After 20 minutes, it is taken out and rolled, and then placed in a 120°C oven for drying for 5 minutes, so that a hydrophilic layer is formed on the surface of the long fiber sliver body, thus obtaining a composite long fiber sliver.

[0041] Example 5 The preparation method of hydrophilic coatings includes the following steps: 0.03 g of silane coupling agent was added to 3 mL of ethanol-deionized water mixture (volume ratio of ethanol to deionized water was 1:3) to prepare a pre-hydrolyzed silane coupling agent solution. 1 g of silk fibroin was added to 60 mL of deionized water and stirred at 600 rpm for 1 h at 40 °C. Then 1.3 g of tetraethyl orthosilicate was added and stirred at 400 rpm for 2 h at 25 °C. The pre-hydrolyzed silane coupling agent solution was then added and stirred for 30 min. Finally, hydrochloric acid (1 mol / L) was added until the pH was 4 to prepare a hydrophilic coating.

[0042] The silane coupling agents include aminosilane coupling agents and polyether-modified silane coupling agents. The aminosilane coupling agent is KH-550, and the polyether-modified silane coupling agent is UM-ET10. The mass ratio of KH-550 to UM-ET10 is 3:1.

[0043] The preparation method of silane coupling agents includes the following steps: KH-550 and UM-ET10 were mixed and stirred evenly to obtain an aminosilane coupling agent.

[0044] The preparation method of polypropylene ultrafine denier composite long fiber sliver includes the following steps: The long fiber sliver body is immersed in a hydrophilic coating at 40°C with a roll weight of 70%. After 20 minutes, it is taken out and rolled, and then placed in a 120°C oven for drying for 5 minutes, so that a hydrophilic layer is formed on the surface of the long fiber sliver body, thus obtaining a composite long fiber sliver.

[0045] Example 6 The difference between Example 6 and Example 3 is that the mass ratio of silk fibroin, tetraethyl orthosilicate, and aminosilane coupling agent is 1:0.8:0.03.

[0046] Example 7 The difference between Example 7 and Example 3 is that the mass ratio of silk fibroin, tetraethyl orthosilicate, and aminosilane coupling agent is 1:1.6:0.03.

[0047] Example 8 The difference between Example 8 and Example 3 is that an antibacterial reinforcing layer is provided on the side of the hydrophilic layer away from the long fiber strip body.

[0048] The preparation method of the antibacterial reinforced coating includes the following steps: 10g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added to 100mL of isopropanol-deionized water mixture (volume ratio of isopropanol to deionized water was 2:1). After stirring evenly, glacial acetic acid was added to make the pH 5, thus obtaining an antibacterial reinforced coating.

[0049] The preparation method of polypropylene ultrafine denier composite long fiber sliver includes the following steps: S1. The long fiber sliver body is immersed in a hydrophilic coating at 40°C with a roll rate of 70%. After 20 minutes, it is taken out and rolled, and then placed in an oven at 120°C for 5 minutes to dry, so that a hydrophilic layer is set on the surface of the long fiber sliver body, thereby obtaining the primary composite long fiber sliver. S2. The primary composite long fiber sliver is immersed in an antibacterial reinforcing coating at 60°C with a roll rate of 70%. After 30 minutes, it is taken out and rolled, and then placed in a 100°C oven for drying for 10 minutes, so that an antibacterial reinforcing layer is set on the hydrophilic layer, thereby obtaining the composite long fiber sliver.

[0050] Example 9 The difference between Example 9 and Example 8 is that: dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was prepared by modification. The method for preparing modified dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride includes the following steps: 10 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added to 20 mL of anhydrous toluene and stirred until homogeneous. Then, 5.7 g of polyethylene glycol (PEG-600) was added, and the mixture was heated to 70 °C and stirred until dissolved. Then, 0.05 g of p-toluenesulfonic acid was added, and the mixture was reacted at a constant temperature for 8 hours. After the reaction was completed, the mixture was distilled under reduced pressure, cooled, and washed three times with saturated sodium bicarbonate solution to remove excess p-toluenesulfonic acid. Toluene was then removed by distillation under reduced pressure to obtain modified dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride.

[0051] Example 10 The difference between Example 10 and Example 8 is that: dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was prepared by modification. The method for preparing modified dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride includes the following steps: 10 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added to 20 mL of anhydrous toluene and stirred until homogeneous. Then, 5.2 g of polyethylene glycol (PEG-600) was added, and the mixture was heated to 70 °C and stirred until dissolved. Then, 0.05 g of p-toluenesulfonic acid was added, and the mixture was reacted at a constant temperature for 8 hours. After the reaction was completed, the mixture was distilled under reduced pressure, cooled, and washed three times with saturated sodium bicarbonate solution to remove excess p-toluenesulfonic acid. Toluene was then removed by distillation under reduced pressure to obtain modified dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride.

[0052] Example 11 The difference between Example 11 and Example 8 is that: dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was prepared by modification. The method for preparing modified dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride includes the following steps: 10 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added to 20 mL of anhydrous toluene and stirred until homogeneous. Then, 6.2 g of polyethylene glycol (PEG-600) was added, and the mixture was heated to 70 °C and stirred until dissolved. Then, 0.05 g of p-toluenesulfonic acid was added, and the mixture was reacted at a constant temperature for 8 hours. After the reaction was completed, the mixture was distilled under reduced pressure, cooled, and washed three times with saturated sodium bicarbonate solution to remove excess p-toluenesulfonic acid. Toluene was then removed by distillation under reduced pressure to obtain modified dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride.

[0053] Example 12 The difference between Example 12 and Example 9 is that the mass ratio of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride to polyethylene glycol is 1:0.42.

[0054] Example 13 The difference between Example 13 and Example 9 is that the mass ratio of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride to polyethylene glycol is 1:0.72.

[0055] Example 14 The difference between Example 14 and Example 9 is that the antibacterial reinforced coating also includes polyethyleneimine, and the preparation method of the antibacterial reinforced coating includes the following steps: 10g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added to 100mL of isopropanol-deionized water mixture (volume ratio of isopropanol to deionized water was 2:1). After stirring evenly, 0.25g of polyethyleneimine was added and stirred thoroughly. Then, glacial acetic acid was added to make the pH 5, thus obtaining the antibacterial reinforced coating.

[0056] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that no hydrophilic layer is provided on the long fiber strip body.

[0057] Performance testing: Samples of the long fiber slivers obtained in Examples 1-11 and Comparative Example 1 were taken and subjected to the following performance tests.

[0058] 1. Hydrophilicity: The water contact angle of the sample surface was tested using an optical contact angle meter. The sample was washed 30 times and dried according to the method standard of GB / T8629-2001, and then the water contact angle was tested. The test results were recorded in Table 1.

[0059] (2) Antibacterial properties Referring to GB / T20944.3-2008, each sample was tested three times in its initial state and after being washed with water 30 times and dried. The average value was taken, and the test results were recorded in Table 1.

[0060] Table 1 Data Analysis Specifically, comparing Example 2 and Example 1, Example 2 shows better hydrophilic durability and antibacterial durability than Example 1. The difference between Example 2 and Example 1 is that KH-550 is added to the hydrophilic coating. KH-550, together with silk fibroin and silica, forms a "protein-coupling agent-silica" bridging structure, which effectively improves the stability of the hydrophilic layer located in the body of the long fiber strand, thereby improving the hydrophilic durability of the long fiber strand.

[0061] Specifically, considering Examples 3 and 2, Example 3 exhibits superior hydrophilicity and hydrophilic durability compared to Example 2. The difference between Example 3 and Example 2 lies in the fact that the silane coupling agent includes an amino-amino silane coupling agent and a polyether-modified silane coupling agent. The flexibility of the polyether segments in the polyether-modified silane coupling agent counteracts the rigidity of silica, while its hydrophilicity improves the hygroscopicity of the fiber. Thus, through the synergy between the amino-silane coupling agent and the polyether-modified silane coupling agent, the hygroscopicity and stability of the hydrophilic layer located on the long fiber sliver are improved, thereby enhancing the hydrophilicity and hydrophilic durability of the hydrophilic layer located on the long fiber sliver.

[0062] Specifically, considering Examples 8 and 3, Example 3 exhibits superior antibacterial properties and antibacterial durability compared to Example 3. The difference between Example 8 and Example 3 lies in the fact that an antibacterial reinforcing layer is also provided on the long fiber strand body. On one hand, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride itself possesses good antibacterial activity. On the other hand, the unreacted amino groups of KH-550 enhance the binding of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride through electrostatic attraction. The silanoxy group in the molecular structure of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride can undergo a condensation reaction with the hydroxyl groups on the surface of silk fibroin / silica to form Si-OC or Si-O-Si bonds, achieving chemical anchoring. This improves the stability of the antibacterial reinforcing layer on the hydrophilic layer, thereby enhancing the antibacterial properties and antibacterial durability of the long fiber strand.

[0063] Based on the comparison of Examples 9 and 8, the antibacterial properties and antibacterial durability of Example 9 are superior to those of Example 8. The difference between Example 9 and Example 8 is that the treatment of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride with polyethylene glycol enhances the dispersibility of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, effectively improving the antibacterial properties of the antibacterial reinforcement layer. On the other hand, the hydroxyl groups of polyethylene glycol form hydrogen bonds with the amide bonds of silk fibroin, enhancing the stability of the antibacterial reinforcement layer on the hydrophilic layer, thereby improving the antibacterial properties and antibacterial durability of the long fiber strands.

[0064] Specifically, considering Examples 14 and 9, the antibacterial durability of Example 14 is better than that of Example 9. The difference between Example 14 and Example 9 is that the antibacterial enhancer also contains polyethyleneimine, which can effectively enhance the interlayer cross-linking effect, reduce the shedding of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, and improve the stability of the antibacterial enhancement layer on the hydrophilic layer, thereby improving the antibacterial durability of the long fiber strands.

[0065] Specifically, let's look at Example 1 and Comparative Example 1. The hydrophilicity and antibacterial properties of Example 1 and Comparative Example 1 are better than those of Comparative Example 1. The difference between Example 1 and Comparative Example 1 is that the long fiber slivers are treated with a hydrophilic coating formed by silk fibroin and tetraethyl orthosilicate, thereby effectively improving the hydrophilicity of the long fiber slivers.

[0066] The above are all preferred embodiments of the present application, and are not intended to limit the scope of protection of the present application. Therefore, any equivalent changes made based on the structure, shape, and principle of the present application should be included in the scope of protection of the present application.

Claims

1. A polypropylene ultrafine denier composite long fiber sliver, comprising a long fiber sliver body (1), characterized in that: A hydrophilic layer (2) is provided on the long fiber sliver body (1). The hydrophilic layer (2) is formed by curing a hydrophilic coating on the long fiber sliver body. The preparation method of the hydrophilic coating includes the following steps: Silk fibroin was added to deionized water and stirred thoroughly. Then, tetraethyl orthosilicate was added and stirred evenly. Hydrochloric acid was added to adjust the pH to 4 to obtain a hydrophilic coating.

2. The polypropylene ultrafine denier composite long fiber sliver according to claim 1, characterized in that: The hydrophilic coating is prepared by adding a silane coupling agent, and the preparation method of the hydrophilic coating includes the following steps: A pre-hydrolyzed silane coupling agent solution was prepared by adding silane coupling agent to an ethanol-deionized water mixture. Silk fibroin was added to deionized water, stirred thoroughly, and then tetraethyl orthosilicate was added. After stirring evenly, the pre-hydrolyzed silane coupling agent solution was added, and stirring was continued. Hydrochloric acid was added to adjust the pH to 4 to obtain a hydrophilic coating.

3. The polypropylene ultrafine denier composite long fiber sliver according to claim 2, characterized in that: The mass ratio of silk fibroin, tetraethyl orthosilicate and silane coupling agent is 1:(1.1-1.3):0.

03.

4. The polypropylene ultrafine denier composite long fiber sliver according to claim 2, characterized in that: The silane coupling agent includes an aminosilane coupling agent.

5. The polypropylene ultrafine denier composite long fiber sliver according to claim 4, characterized in that: The silane coupling agent also includes a polyether-modified silane coupling agent.

6. The polypropylene ultrafine denier composite long fiber sliver according to claim 2, characterized in that: An antibacterial reinforcement layer (3) is provided on the side of the hydrophilic layer (2) away from the long fiber strip body (1). The antibacterial reinforcement layer (3) is formed by curing an antibacterial reinforcement coating on the hydrophilic layer. The preparation method of the antibacterial reinforcement coating includes the following steps: Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added to a mixture of isopropanol and deionized water, stirred until homogeneous, and then glacial acetic acid was added to adjust the pH to 5 to obtain an antibacterial reinforced coating.

7. The polypropylene ultrafine denier composite long fiber sliver according to claim 6, characterized in that: The modified preparation method of the dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride includes the following steps: Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added to anhydrous toluene and stirred until homogeneous. Polyethylene glycol was then added and stirred thoroughly. P-toluenesulfonic acid was then added to react with the mixture. After the reaction was completed, the mixture was distilled under reduced pressure, cooled, washed, and then distilled under reduced pressure again to obtain modified dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride.

8. The polypropylene ultrafine denier composite long fiber sliver according to claim 7, characterized in that: The mass ratio of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride to polyethylene glycol is 1:(0.52-0.62).

9. The polypropylene ultrafine denier composite long fiber sliver according to claim 7, characterized in that: The antibacterial reinforced coating also includes polyethyleneimine, and the preparation method of the antibacterial reinforced coating includes the following steps: Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was added to a mixture of isopropanol and deionized water, stirred until homogeneous, and then polyethyleneimine was added and stirred thoroughly. Finally, glacial acetic acid was added to adjust the pH to 5 to obtain an antibacterial reinforced coating.

10. A method for preparing polypropylene ultrafine denier composite long fiber sliver as described in any one of claims 1-9, comprising the following steps: S1. The long fiber sliver body is immersed in a hydrophilic coating. After immersion, it is taken out and rolled, and then heat-treated to make the surface of the long fiber sliver body have a hydrophilic layer, thereby obtaining the primary composite long fiber sliver. S2. The primary composite long fiber sliver is immersed in the antibacterial reinforcing coating. After immersion, it is taken out and rolled, and then heat-treated to form an antibacterial reinforcing layer on the hydrophilic layer, thereby producing the composite long fiber sliver.

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