Polyamide spinning oil, method for preparing the same, and polyamide fiber

Abstract

The present application belongs to the technical field of polyamide fiber preparation, and particularly relates to a polyamide spinning oil, a preparation method thereof and polyamide fiber. The polyamide spinning oil comprises the following raw material components in parts by weight: polyethylene glycol sorbitol hexaoleate 15-25 parts, polyethylene glycol 15-hydroxystearate 10-25 parts, triethanolamine di(octadecanoic acid) ester 10-20 parts, alkyl phenol polyoxyethylene quaternary ammonium salt 5-10 parts, chitosan quaternary ammonium salt 5-10 parts, tri-glycerol monostearate 20-30 parts, 2(3)-tert-butyl-4-hydroxyanisole 2-20 parts, anti-phenolic yellowing agent APY 2-5 parts, penetrant JFC 3-6 parts and bis(2,6-diisopropylphenyl)carbodiimide 1-5 parts. The polyamide spinning oil of the present application is designed rationally, which significantly improves the smoothness, flexibility, bundling, anti-static property, yellowing resistance and other properties of the polyamide spinning fiber, and also has the synergistic effects of antibacterial, antioxidant degradation and hydrolysis resistance, thereby improving the product performance of the polyamide fiber.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of polyamide fiber preparation, and particularly relates to a polyamide spinning oil and a preparation method thereof and a polyamide fiber. BACKGROUND

[0002] Polyamide fiber is an important synthetic fiber, also widely known as nylon. The main raw material of polyamide fiber is polyamide, and the molecular structure of this polymer contains repeating amide groups. These amide groups make nylon fiber have excellent strength, wear resistance, flexibility and chemical corrosion resistance. Its excellent performance and wide application prospect make it occupy an important position in the field of synthetic fibers.

[0003] The manufacturing process of polyamide fiber includes polymerization, spinning and subsequent processing, etc. Among them, spinning is the process of converting polymer melt or solution into fiber. In the spinning process, oil is a key auxiliary agent. The purposes of using oil mainly include the following points: (1) Lubrication: In the spinning process, friction will occur between the fiber and the mechanical equipment. If the friction is too large, it is easy to cause fiber breakage or produce defective products. Oil can form a lubricating film on the surface of the fiber and the equipment, reduce the friction, improve the smoothness and flexibility of the fiber, so that the fiber can smoothly pass through the spinning machine, thereby reducing the broken yarn and improving the production efficiency. (2) Prevent static electricity: In the spinning process, static electricity is easily generated when the fiber contacts with the equipment. Static electricity can cause attraction between fibers and adsorption of fibers and equipment surfaces, resulting in fiber agglomeration, spinning quality decline or even spark to cause safety hazards. The addition of antistatic agent in the oil can effectively reduce the generation and influence of static electricity, improve the fiber bundling, and ensure the smooth spinning of the fiber. (3) Reduce fiber breakage: In the spinning process, the fiber may be subjected to tension, extrusion and other forces, which can easily cause breakage. The use of oil can improve the softness and ductility of the fiber, reduce the breakage of the fiber under stress, and improve the spinning success rate. (4) Protect equipment: The parts of the spinning equipment are easy to wear and tear under long-time high-speed operation. Oil can form a protective film to reduce the wear and corrosion of the equipment and prolong the service life of the equipment. (5) Adjust the performance of the fiber: Oil can adjust the surface tension, surface energy and other physical properties of the fiber, thereby affecting the moisture absorption, softness, gloss and other characteristics of the fiber, so that the final product has better quality and performance.

[0004] However, in addition to this, polyamide fiber is prone to yellowing due to oxidation during the molding process. In addition, polyamide fiber has the characteristics of easy water absorption and easy hydrolysis of amide bond. In addition, polyamide fiber is prone to bacterial growth and bacterial contamination. In view of the above, it is necessary to develop an oil that has the performance of conventional oil, and also has the performance of antibacterial, antioxidant and hydrolysis resistance.

[0005] Chinese patent CN104947421A discloses a new type of nylon spinning oil, which is composed of the following components in parts by weight: pentaerythritol stearate: 20-30, potassium lauryl ether phosphate: 0.1-0.3, isostearic acid: 3-6, coconut diethanolamide: 2-5, polydimethylsiloxane: 0.1-0.3, sodium dioctyl sulfosuccinate: 1-3, lauryl oleate: 10-20, vinyl stearate: 10-20, and water: 200-400. The formula does not have antibacterial, antioxidant, and hydrolysis-resistant designs, so it does not have antibacterial, antioxidant, and hydrolysis-resistant properties. The prepared fiber is easily contaminated by microorganisms, and long-term storage can also cause the fiber strength and other properties to decrease. The oil agent stability is also poor, which is not conducive to long-term storage.

[0006] Chinese patent CN103422342A provides a polyamide fiber oil agent, which is characterized by being mixed by the following components in percentage based on the total weight of the polyamide fiber oil agent: white oil, 28-30%; stearic acid, 5-7%; MOA3, 4-5%; succinic acid penetrant T, 19-21%; triethanolamine, 5-6%; lauric acid diester, 4-5%; oleic acid, 5-7%; Tween (80), 3-5%; MOA3PK, 8-9%; polyoxyethylene alkyl fatty ester, 7-8%; butyl cellosolve, 2-5%. The polyamide fiber oil agent of the patent has appropriate smoothness and high antistatic properties, and has good application prospects, but does not have antibacterial, antioxidant, and hydrolysis-resistant designs.

[0007] Chinese patent CN115897216A provides a degradable oil agent for nylon high-temperature-resistant and yellowing-resistant spinning and a preparation method thereof, which comprises 1-2 parts of coated composite nano-aerogel, 5-10 parts of zinc chloride solution, 0.5-1.2 parts of cetyltrimethylammonium bromide solution, 2-5 parts of sodium hydroxide, 6-10 parts of antistatic agent, 5-8 parts of emulsifier, 80-100 parts of base oil, 3-6 parts of bundling agent, 1-2 parts of defoaming agent, and 0.8-1.5 parts of polyether silicone oil. The oil agent of the patent has good degradation performance, but does not have antibacterial, antioxidant, and hydrolysis-resistant designs.

[0008] In view of this, the present application is proposed. SUMMARY

[0009] The present application aims to provide a polyamide spinning oil agent, a preparation method thereof, and a polyamide fiber. The polyamide spinning oil agent is designed rationally, significantly improves the smoothness, softness, bundling, antistatic property, and yellowing resistance of the polyamide spinning fiber, and has the synergistic effects of antibacterial, antioxidant degradation, and hydrolysis resistance. The product performance and stability of the polyamide fiber are ultimately improved, thereby effectively solving a series of problems of the polyamide fiber in the spinning process.

[0010] To achieve the above object, the present application provides the following technical solutions.

[0011] In one aspect, a polyamide spinning oil is provided, comprising the following raw material components in parts by weight:

[0012] Polyethylene glycol sorbitol hexaoleate 15-25 parts, polyethylene glycol 15-hydroxystearate 10-25 parts, triethanolamine di(octadecanoic acid) ester 10-20 parts, alkyl phenol polyoxyethylene quaternary ammonium salt 5-10 parts, chitosan quaternary ammonium salt 5-10 parts, tri glycerol monostearate 20-30 parts, 2(3)-tert-butyl-4-hydroxyanisole 2-20 parts, anti-phenolic yellowing agent APY 2-5 parts, penetrant JFC 3-6 parts, and bis(2,6-diisopropylphenyl) carbodiimide 1-5 parts.

[0013] In an alternative embodiment, the following raw material components are included in parts by weight:

[0014] Polyethylene glycol sorbitol hexaoleate 20 parts, polyethylene glycol 15-hydroxystearate 20 parts, triethanolamine di(octadecanoic acid) ester 15 parts, alkyl phenol polyoxyethylene quaternary ammonium salt 7 parts, chitosan quaternary ammonium salt 7 parts, tri glycerol monostearate 25 parts, 2(3)-tert-butyl-4-hydroxyanisole 7 parts, anti-phenolic yellowing agent APY 4 parts, penetrant JFC 5 parts, and bis(2,6-diisopropylphenyl) carbodiimide 2 parts.

[0015] In an alternative embodiment, the following steps are included:

[0016] S1, polyethylene glycol sorbitol hexaoleate and polyethylene glycol 15-hydroxystearate are mixed in proportion, and after stirring uniformly, a mixture A is obtained;

[0017] S2, triethanolamine di(octadecanoic acid) ester is added to the mixture A obtained in step S1, and after stirring uniformly, a mixture B is obtained;

[0018] S3, alkyl phenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt are sequentially added to the mixture B obtained in step S2, and after stirring uniformly, a mixture C is obtained;

[0019] S4, tri glycerol monostearate is slowly added to the mixture C obtained in step S3, and after stirring uniformly, a mixture D is obtained;

[0020] S5, 2(3)-tert-butyl-4-hydroxyanisole and anti-phenolic yellowing agent APY are sequentially added to the mixture D obtained in step S4, and after stirring uniformly, a mixture E is obtained;

[0021] S6, adding the penetrating agent JFC, bis (2, 6- diisopropylphenyl) carbodiimide, to the mixture E obtained in step S5, stirring uniformly, to obtain the polyamide spinning finish.

[0022] In an alternative embodiment, in step S1, the stirring process conditions are: constant temperature at 55-65℃, high speed stirring for 30-35min, stirring rate of 800-850rpm;

[0023] And / or, in step S2, the stirring process conditions are: stirring at a rate of 900-950rpm for 20-25min.

[0024] In an alternative embodiment, in step S3, the stirring process conditions are: stirring at a rate of 1200-1250rpm for 30-35min; after the mixture C system becomes viscous, the stirring rate is reduced to 850-900rpm.

[0025] In an alternative embodiment, in step S4, the stirring process conditions are: stirring at a rate of 500-1000rpm for 30-35min; then the rate is increased to 1200-1250rpm, and stirring is continued for 20-25min.

[0026] In an alternative embodiment, in step S5, the stirring process conditions are: stirring at a rate of 1500-1550rpm for 30-35min;

[0027] And / or, in step S6, the stirring process conditions are: stirring at a rate of 1500-1550rpm for 40-45min.

[0028] In another aspect, a polyamide fiber is also provided, characterized in that it is made of the polyamide spinning finish described above and prepared by the preparation method described in any one of the above aspects.

[0029] In an alternative embodiment, the polyamide fiber has a fineness of 1-600dtex; and / or, a breaking strength of 3-10cN / dtex, an elastic modulus of 10-50cN / dtex, and an elongation at break of 20-50%.

[0030] In another aspect, a preparation method of the polyamide fiber described above is provided, which comprises adding the polyamide spinning finish into the sizing tank of the oiling machine, then immersing the unsized synthetic fiber into the polyamide spinning finish, and passing through the sizing tank of the oiling machine at a drawing speed of 5-2000m / min, and winding after high-drawing, to obtain the polyamide fiber.

[0031] Compared with the prior art, the technical scheme of the present application has at least the following technical effects:

[0032] (1) The polyamide spinning oil of the present application significantly improves the smoothness, softness, bundling, antistatic property, yellowing resistance and other properties of the polyamide spun fiber through rational design, and also has the synergistic effects of antibacterial, antioxidant degradation and hydrolysis resistance, rather than the mechanical accumulation of single effect, thereby ultimately improving the product performance and stability of the polyamide fiber, effectively solving a series of problems of the polyamide fiber in the spinning process, and playing a crucial role in the stability of the fiber spinning process, the improvement of fiber quality and the improvement of production efficiency, which not only ensures the smooth progress of the spinning process, improves the quality and performance of the product, but also improves the production efficiency, reduces the production cost, and promotes the sustainable development of the enterprise.

[0033] (2) The polyamide spinning oil of the present application ensures uniform oiling and reduces splashing when used, and is suitable for the smoothness of high-speed spinning production; it has good spinnability, effectively improves the fiber quality, and makes the first-class fiber quality rate of the fiber reach more than 97%, significantly improving the quality and production efficiency of the fiber. Moreover, the winding and unwinding process is more smooth; it meets the requirements of the processes of unwinding, stretching, winding and false twisting in the fiber processing process, maintains the uniformity of the false twisting tension, thereby ensuring the stability of the spinning process, reducing the fiber lint and broken end phenomenon, and there is no oil agent impurity deposition and color masterbatch pigment precipitation phenomenon on the post-spinning equipment.

[0034] (3) The spinning oil of the present application has a wetting time of 0.5-10 seconds and a surface tension of 2-40 N / m for the polyamide fiber, has excellent lubricating property, excellent adsorption property and good aggregation property, effectively reduces the white powder generated by friction in the nylon yarn production process; in addition, the viscosity of the oil is less affected by temperature, is not easy to produce oil smoke after heating, and has less coke deposition on the heating roller surface, and is easy to clean. The polyamide fiber prepared by using the oil of the present application has good bundling, stretching and molding, the yarn beam is bright, the oil agent has little odor, the spinning process is stable, and the product quality can meet the use requirements. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical scheme and advantages of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. It should be understood by those skilled in the art that the embodiments are only used to help understand the present application, and should not be regarded as a specific limitation on the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application. The process parameters not specified in the following embodiments are usually according to the conventional conditions.

[0036] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as exactly that endpoint. Any values that fall within the range of values are included in the disclosed ranges. Whenever a numerical range is indicated, it is meant to include all values and sub-ranges within the range. Numerical ranges are indicated according to their proximity to their endpoints, and all quantities and dimensions disclosed herein can be one of or a combination of a range and an amount end-point.

[0037] According to a first aspect of the present application, there is provided a polyamide spinning oil comprising the following raw material components by weight parts:

[0038] Polyethylene glycol sorbitol hexaoleate 15-25 parts (such as 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts), polyethylene glycol 15-hydroxystearate 10-25 parts (such as 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts), triethanolamine di(octadecanoate) 10-20 parts (such as 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts), alkylphenol polyoxyethylene quaternary ammonium salt 5-10 parts (such as 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts), chitosan quaternary ammonium salt 5-10 parts (such as 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts), tripolyglycerol monostearate 20-30 parts (such as 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts), 2(3)-tert-butyl-4-hydroxyanisole 2-20 parts (such as 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts), anti-phenolic yellowing agent APY 2-5 parts (such as 2 parts, 3 parts, 4 parts, 5 parts), penetrant JFC 3-6 parts (such as 3 parts, 4 parts, 5 parts, 6 parts), and bis(2,6-diisopropylphenyl)carbodiimide 1-5 parts (such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts).

[0039] Polyamide fibers are prone to yellowing during processing due to oxidation, which is mainly caused by the oxidation reaction between polyamide fibers and oxygen at high temperature and high humidity, leading to the breakage of chemical bonds in the molecular structure of polyamide, producing products containing phenolic groups, thus causing the yellowing phenomenon on the surface of the fiber. Polyamide fibers also have the characteristics of easy water absorption and amide bond hydrolysis, which is due to the presence of a large number of polar amide groups (-CONH-) in their molecular structure, which can form hydrogen bonds with water molecules. Therefore, during the processing, polyamide fibers are prone to absorb moisture from the surrounding environment, leading to fiber swelling and even hydrolysis, affecting its physical properties and dimensional stability. The amide bond (-CONH-) in the polyamide molecule is susceptible to hydrolysis, especially in a high-temperature, high-humidity environment. Hydrolysis can cause the breakage of polyamide molecular chains, reducing the molecular weight and mechanical properties of the fiber, and even leading to the destruction of the fiber. Polyamide fibers are prone to bacterial growth and contamination, mainly due to the following factors: (1) Water absorption: Polyamide fibers have strong water absorption, which makes the surface of the fiber wet, providing a moist environment for bacterial growth. Bacteria usually need water to grow and reproduce, so the increased water absorption on the surface of the fiber increases the possibility of bacterial growth. (2) Surface morphology: The micro-morphology of the surface of polyamide fibers can also promote the attachment and growth of bacteria, for example, the small bumps and grooves on the surface of the fiber or the inter-fiber voids can provide small spaces for bacterial growth.

[0040] The inventors, for the above reasons, successfully developed a new type of antibacterial, oxidation-resistant and hydrolysis-resistant polyamide spinning oil by reasonably designing the oil formula, including one or more of smoothing agents, additives with synergistic properties such as antibacterial, antistatic, antioxidant, oxidation-resistant degradation, yellowing-resistant, hydrolysis inhibitors, etc. In the polyamide spinning oil formula of the present application, polyethylene glycol sorbitol hexaoleate is used as a smoothing agent, polyethylene glycol 15-hydroxystearate is used as a softening agent, triethanolamine di(octadecanoic acid) ester is used as a bunching agent, and tri glycerol monostearate is used as a surfactant. The organic combination of alkyl phenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt exhibits synergistic effects of antistatic and antibacterial. Both of these substances have certain antibacterial and antistatic properties, but they can enhance each other after combination, producing stronger comprehensive effects. Specifically, alkyl phenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt are both cationic surfactants, with the ability to adsorb on the surface of fibers to form protective films, which can effectively block the generation and accumulation of static electricity, thereby reducing the static charging phenomenon of fiber materials. Alkyl phenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt also have good antibacterial activity, which can inhibit and kill bacteria, fungi and other microorganisms. They can destroy the cell wall or cell membrane of microorganisms, block the growth and reproduction of microorganisms, thereby achieving the effect of antibacterial. The synergistic effect is as follows: when alkyl phenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt are organically combined, their antibacterial and antistatic effects can be enhanced. This is because they can form more stable and uniform protective films on the surface, while increasing the density of cations, making the inhibition effect of static electricity and microorganisms more significant. Therefore, the organic combination of alkyl phenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt not only provides dual functions of antistatic and antibacterial, but also enhances their comprehensive performance through synergistic effect, providing an effective solution for antistatic and antibacterial products in the application field of fiber materials.

[0041] In particular, 2(3)-tert-butyl-4-hydroxyanisole as a fat-soluble antioxidant, thermal stability is good, help to reduce the fiber in the production and subsequent use of oxidative degradation, tert-butyl-4-hydroxyanisole has strong antioxidant capacity and antibacterial capacity, can inhibit staphylococcus aureus, aspergillus flavus growth. Alkyl phenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt has good antibacterial activity, can inhibit and kill bacteria, fungi and other microorganisms. Therefore, the two substances have synergistic antibacterial effect, realize the organic combination of antibacterial and antioxidant. 2(3)-tert-butyl-4-hydroxyanisole is a lipophilic compound, has antibacterial activity to mold and gram-positive bacteria. Also has antioxidant effect: 2(3)-tert-butyl-4-hydroxyanisole as an antioxidant, can effectively prevent the fiber raw materials in the spinning process by oxidation. Add 2(3)-tert-butyl-4-hydroxyanisole can stabilize the active groups in the polyamide fiber raw materials, inhibit the occurrence of oxidation reaction, prolong the service life of the fiber. In the spinning process, the fiber raw materials are easily affected by oxygen, light, heat and other factors in the external environment and oxidized, which affects the quality and performance of the fiber. By adding antioxidant such as 2(3)-tert-butyl-4-hydroxyanisole, the quality of the fiber raw materials can be effectively protected, and the oxidation damage in the spinning process can be prevented, and the quality and yield of the fiber can be improved. Improve product stability: 2(3)-tert-butyl-4-hydroxyanisole as an antioxidant, can improve the stability of the fiber spinning oil. In the spinning process, the performance of the spinning oil may be affected by oxidation, which affects the processing quality of the fiber. By adding antioxidant, such as 2(3)-tert-butyl-4-hydroxyanisole, the performance stability of the spinning oil can be effectively maintained, and the smooth progress of the fiber processing process is ensured.

[0042] In particular, bis(2,6-diisopropylphenyl)carbodiimide (DCDPA) plays an important role as a hydrolysis-resistant agent in oil agents. Bis(2,6-diisopropylphenyl)carbodiimide in oil agents can form a protective film on the surface of fiber materials, blocking the penetration of water and oxygen, reducing the contact between fiber molecular chains and water molecules, and thus slowing down the occurrence of hydrolysis reactions. It can also compete with water molecules for adsorption, reducing the diffusion and penetration of water molecules in the fiber material, thereby reducing the rate of hydrolysis reactions. It can also chemically react with active groups such as hydroxyl groups in polyamide fiber materials, stabilizing the fiber structure and reducing the sensitivity of hydrolysis reactions. This is mainly reflected in the following aspects. Preventing hydrolysis reactions: In fiber oil agents, DCDPA can inhibit the hydrolysis of fibers and other organic substances. The components in fiber oil agents are often affected by water and other conditions in the environment and undergo hydrolysis reactions, leading to a decrease in the performance of fiber oil agents. DCDPA can slow down or prevent these hydrolysis reactions from occurring, thereby improving the stability and durability of fiber oil agents. Bis(2,6-diisopropylphenyl)carbodiimide can form a protective film on the surface of fiber materials, blocking the penetration of water and oxygen, reducing the contact between fiber molecular chains and water molecules, and thus slowing down the occurrence of hydrolysis reactions. It can also compete with water molecules for adsorption, reducing the diffusion and penetration of water molecules in the fiber material, thereby reducing the rate of hydrolysis reactions. It can also chemically react with active groups such as hydroxyl groups in fiber materials, stabilizing the fiber structure and reducing the sensitivity of hydrolysis reactions. Enhancing the performance of oil agents: DCDPA as a hydrolysis-resistant agent can also enhance the performance of fiber oil agents, allowing them to maintain good results in humid or high-temperature environments. By reducing the occurrence of hydrolysis reactions, DCDPA helps maintain the viscosity, lubricity, and antioxidant properties of fiber oil agents, extending their service life. Improving processing efficiency: Fiber oil agents play a role in lubricating and protecting fibers during textile processing, and DCDPA as a hydrolysis-resistant agent can ensure that fiber oil agents remain stable during processing and are not easily affected by hydrolysis, thereby improving processing efficiency and product quality. Improving fiber properties: The use of DCDPA improves the hydrolysis resistance of fibers and also improves the softness, gloss, and wear resistance of fibers, making fiber products have better hand feel and appearance. Bis(2,6-diisopropylphenyl)carbodiimide as a hydrolysis-resistant agent in fiber oil agents plays an important role in the stability, performance, and processing efficiency of fiber oil agents, helping to improve the quality and service life of fiber products.

[0043] The penetrant JFC plays a key role in the fiber spinning oil, its main functions include the following aspects: improve the wettability of fiber raw materials: penetrant JFC can increase the wettability of fiber raw materials, so that it is easier to be wetted and processed. In the spinning process, fiber raw materials need to be fully contacted and wetted with oil to ensure smooth flow and uniform dispersion of fibers. As a penetrant, JFC can reduce the surface tension between oil and water, promote the penetration and wetting of oil, and improve the processing efficiency of fiber raw materials. Enhance the permeability of oil: penetrant JFC can also enhance the permeability of fiber spinning oil, making it easier to penetrate the internal structure of fiber raw materials. Fiber raw materials often have complex structure and porosity, and oil needs to quickly penetrate and fully cover each fiber to ensure uniform distribution and effective lubrication of oil. JFC can reduce the surface tension of oil, increase its penetration ability inside the fiber raw materials, and improve the dispersibility and coverage of oil. Promote the stretching and extension of fibers: fibers need to undergo stretching and extension during spinning to form long and thin fiber filaments. Penetrant JFC can reduce the friction between fibers during spinning, promote the stretching and extension of fibers, and help produce finer and more uniform fiber filaments, improving the tensile properties of fibers and the quality of products.

[0044] The anti-phenolic yellowing agent APY in the fiber oil mainly includes the following aspects: the anti-phenolic yellowing agent APY can effectively block the free amino group on the polyamide fiber, prevent the fiber from absorbing butylated hydroxytoluene nitrophenol derivatives, etc. Anti-phenolic yellowing agent APY can effectively prevent or slow down the oxidation reaction of fiber raw materials with oxygen, protect fiber raw materials from oxidative damage, improve the durability and stability of fibers, and prolong the service life of fibers. Since fibers are easily affected by external environmental factors such as light and oxygen, yellowing reaction occurs, resulting in changes in the color of the fiber. Anti-phenolic yellowing agent APY can inhibit or slow down the occurrence of this yellowing reaction, maintain the original color and appearance of fiber raw materials, and improve the quality of fiber products. It can also stabilize the active ingredients in the fiber oil, prolong the effective use period of the oil, and ensure its stability and performance during processing. Anti-phenolic yellowing agent APY can reduce the content of phenolic substances, reduce the cleaning frequency of equipment, and improve the stability and processing efficiency of the production line. Anti-phenolic yellowing agent APY helps to reduce the content of phenolic substances in fiber raw materials and fiber products caused by oxidation, reduces the occurrence of oxidation reaction, thereby improving the quality, color and appearance of fiber products. Therefore, whether for fiber processing or subsequent fiber post-processing, the anti-phenolic yellowing agent APY in the oil is of great significance, mainly including antioxidant, anti-yellowing, stabilizing fiber oil, improving processing efficiency and improving fiber product quality, etc. It is an important functional additive.

[0045] The weight parts in the present application mainly include disclosed numerical ranges, any numerical value (including integers and decimals) within the disclosed range or the interval of any two numerical values, or discontinuous intervals, also include values or numerical ranges close to the end values of the numerical range which can be expected to have similar effects, for example, 5-10 parts, not only including 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts and the interval of any two parts, and for other numerical ranges, not one by one, are included in the present application. Therefore, the present application also includes any sub-range of the directly disclosed numerical range or any specific numerical value therein.

[0046] In order to further optimize the curative effect of the polyamide spinning oil, the present application studies the influence degree of different proportions of various raw material components on the effect, and respectively obtains more optimal raw material component proportions, polyethylene glycol sorbitol hexaoleate 20 parts, polyethylene glycol 15-hydroxystearate 20 parts, triethanolamine di(octadecanoate) 15 parts, alkyl phenol polyoxyethylene quaternary ammonium salt 7 parts, chitosan quaternary ammonium salt 7 parts, tripolyglycerol monostearate 25 parts, 2(3)-tert-butyl-4-hydroxyanisole 7 parts, anti-phenolic yellowing agent APY 4 parts, penetrant JFC 5 parts and bis(2,6-diisopropylphenyl)carbodiimide 2 parts.

[0047] The polyamide spinning oil of the present application can be directly used, or can be prepared into an emulsion for use, when prepared into an aqueous emulsion, the aqueous emulsion concentration is 10±2%; the water for preparation is soft water, the hardness is less than 1 pg / g, and the pH value of the acidity and alkalinity is 6.5-7.5. The metered components are slowly added into the soft water according to the emulsion concentration requirements, and can be used under the condition of 20-60℃, high-speed stirring or ultrasonic for 5-60 min, the stirring speed is 1500-3000 rpm, or the ultrasonic power is 100-300 W.

[0048] According to the second aspect of the present application, a preparation method of the above-mentioned polyamide spinning oil is provided, including the following steps:

[0049] S1, polyethylene glycol sorbitol hexaoleate and polyethylene glycol 15-hydroxystearate are mixed in proportion, and after stirring uniformly, a mixture A is obtained;

[0050] S2, triethanolamine di(octadecanoate) is added into the mixture A obtained in step S1, and after stirring uniformly, a mixture B is obtained;

[0051] S3, alkyl phenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt are sequentially added into the mixture B obtained in step S2, and after stirring uniformly, a mixture C is obtained;

[0052] S4, tripolyglycerol monostearate is slowly added into the mixture C obtained in step S3, and after stirring uniformly, a mixture D is obtained;

[0053] S5, adding 2(3)-tert-butyl-4-hydroxyanisole and anti-phenolic yellowing agent APY into the mixture D obtained in step S4 in sequence, and stirring to obtain mixture E;

[0054] S6, adding penetrating agent JFC and bis(2,6-diisopropylphenyl)carbodiimide into the mixture E obtained in step S5, and stirring to obtain the polyamide spinning finish.

[0055] In the above preparation method, as a preferred embodiment, in step S1, the stirring process is performed at a constant temperature of 55-65°C for 30-35 min at a stirring speed of 800-850 rpm.

[0056] Alternatively, in step S2, the stirring process is performed at a stirring speed of 900-950 rpm for 20-25 min.

[0057] Alternatively, in step S3, the stirring process is performed at a stirring speed of 1200-1250 rpm for 30-35 min; after the mixture C becomes viscous, the stirring speed is reduced to 850-900 rpm.

[0058] Alternatively, in step S4, the stirring process is performed at a stirring speed of 500-1000 rpm for 30-35 min; then the stirring speed is increased to 1200-1250 rpm, and the stirring is continued for 20-25 min.

[0059] Alternatively, in step S5, the stirring process is performed at a stirring speed of 1500-1550 rpm for 30-35 min.

[0060] Alternatively, in step S6, the stirring process is performed at a stirring speed of 1500-1550 rpm for 40-45 min.

[0061] According to a third aspect of the present application, there is provided a polyamide fiber prepared by using the polyamide spinning finish and the preparation method described above.

[0062] In the above polyamide fiber, as a preferred embodiment, the polyamide fiber has a fineness of 1-600 dtex, for example, the polyamide fiber can have a fineness of 50 dtex, 60 dtex, 70 dtex, 80 dtex, 100 dtex, 150 dtex, 110 dtex, 120 dtex, 130 dtex, 200 dtex, 30 dtex, 400 dtex, 500 dtex, 550 dtex or 600 dtex, etc.; a breaking strength of 3-10 cN / dtex, for example, the breaking strength can be 3 cN / dtex, 6 cN / dtex, 8 cN / dtex, 9 cN / dtex or 10 cN / dtex, etc. The elastic modulus is 10-50 cN / dtex, for example, the elastic modulus can be 10 cN / dtex, 15 cN / dtex, 20 cN / dtex, 24 cN / dtex, 30 cN / dtex, 35 cN / dtex, 39 cN / dtex, 40 cN / dtex, 45 cN / dtex or 50 cN / dtex, etc. The elongation at break is 20-50%. The strength of the polyamide fiber prepared by the general conventional oil agent is generally 2-6 cN / dtex, and the modulus is generally 20-30 cN / dtex, and the polyamide fiber provided by the embodiment of the present application has better performance than the polyamide fiber in the prior art.

[0063] According to a fourth aspect of the present application, a method for preparing the above polyamide fiber is provided, characterized in that the method comprises adding the polyamide spinning oil agent into the sizing tank of the oiling machine, then immersing the unsized synthetic fiber into the polyamide spinning oil agent, and passing through the sizing tank of the oiling machine at a drawing speed of 5 m / min-2000 m / min, and after high-drawing, winding to obtain the polyamide fiber.

[0064] The present application will be described in detail below with reference to the embodiments of the present application. Each example is provided by way of explanation of the present application and is not intended to limit the present application. In fact, those skilled in the art will appreciate that modifications and variations to the present application can be made without departing from the scope or spirit of the present application. For example, features shown or described as part of one embodiment can be used in another embodiment to yield still a further embodiment. It is, therefore, desired that the present application be deemed as including all such modifications and variations as fall within the scope of the appended claims and their equivalents.

[0065] In the embodiments of the present application, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are commercially available unless otherwise specified.

[0066] In the following examples,

[0067] Polyethylene glycol sorbitol hexaoleate was purchased from Sigma Aldrich Reagent Co., Ltd., with the model number 466409.

[0068] Polyethylene glycol 15-hydroxystearate was purchased from Shanghai Aladdin Biochem Technology Co., Ltd., with the model number K487242.

[0069] Triethanolamine di(octadecanoate) was purchased from Xi'an Ziyue Biological Co., Ltd., with the model number Q-0175039.

[0070] Alkylphenol polyoxyethylene-based quaternary ammonium salt was purchased from Xiya Reagent, with the model number A16677.

[0071] Chitosan quaternary ammonium salt was purchased from Luoen Reagent Co., Ltd., with the model number R140174.

[0072] Triacylglycerol monostearate was purchased from Luoen Reagent Co., Ltd., with the model number R121821.

[0073] 2(3)-tert-butyl-4-hydroxyanisole was purchased from Shanghai Macklin Reagent Co., Ltd., with the model number B802177.

[0074] Antiphellowning agent APY was purchased from Guangzhou Ruiqi Chemical Technology Co., Ltd., with the model number RICHFIX APY.

[0075] Penetrant JFC was purchased from Guangdong Runhong Chemical Co., Ltd., with the model number JFC-1.

[0076] Bis(2,6-diisopropylphenyl)carbodiimide was purchased from Beijing Bailingwei Reagent Co., Ltd., with the model number 421434.

[0077] AZ-60 oil agent, Sanyo Co., Ltd., Japan, with the model number AZ-60.

[0078] ABTS, namely 2,2'-azino-bis(3-ethyl-benzothiazoline-6-sulfonic acid) diammonium salt, was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd., with the model number TMLT18908G1.

[0079] Potassium persulfate was purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd., with the model number 10017428.

[0080] Example 1

[0081] This example provides a polyamide spinning oil, and the content of each component is as follows:

[0082] Polyethylene glycol sorbitol hexaoleate 20 parts, polyethylene glycol 15-hydroxystearate 20 parts, triethanolamine di(octadecanoate) 15 parts, alkylphenol polyoxyethylene quaternary ammonium salt 7 parts, chitosan quaternary ammonium salt 7 parts, tripolyglycerol monostearate 25 parts, 2(3)-tert-butyl-4-hydroxyanisole 7 parts, anti-phenolic yellowing agent APY 4 parts, penetrant JFC 5 parts, and bis(2,6-diisopropylphenyl)carbodiimide 2 parts.

[0083] The preparation method of the polyamide spinning finish of the present embodiment is as follows:

[0084] S1: Polyethylene glycol sorbitol hexaoleate and polyethylene glycol 15-hydroxystearate are added to a stirrer, and stirred at a constant temperature of 60°C at a high speed for 30 minutes, with a rotation speed of 800 rpm, to obtain a mixture 1;

[0085] S2: Triethanolamine di(octadecanoate) is added to the mixture 1 of step S1, and stirred at a rotation speed of 900 rpm for 20 minutes, to obtain a mixture 2;

[0086] S3: Alkylphenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt are added to the mixture 2 of step S2, and stirred at a rotation speed of 1200 rpm for 30 minutes, to obtain a mixture 3, and when the mixture 3 system becomes viscous, the stirring rotation speed is reduced to 900 rpm;

[0087] S4: Tripolyglycerol monostearate is slowly added to the mixture 3 of step S3, and after stirring for 30 minutes, the rotation speed is increased to 1200 rpm, and stirring is continued for 20 minutes, to obtain a mixture 4;

[0088] S5: 2(3)-tert-butyl-4-hydroxyanisole and anti-phenolic yellowing agent APY are added to the mixture 4 of step S4, and stirred at a rotation speed of 1500 rpm for 30 minutes, to obtain a mixture 5;

[0089] S6: Penetrant JFC and bis(2,6-diisopropylphenyl)carbodiimide are added to the mixture 5 of step S5, and stirred at a rotation speed of 1500 rpm for 40 minutes, to obtain a spinning finish.

[0090] The present embodiment also provides a polyamide fiber made of the polyamide spinning finish of the present embodiment, and the preparation method is as follows: the polyamide spinning finish is added to the sizing tank of the oiling machine, then the unsized synthetic fiber is immersed in the polyamide spinning finish, and is passed through the sizing tank of the oiling machine at a drawing speed of 2000 m / min, 1600 m / min, 1400 m / min, or 1200 m / min, and after high-drawing, the polyamide fiber is wound up.

[0091] The polyamide fiber of the present example was subjected to performance testing (breaking strength, breaking elongation, modulus of elasticity, elongation coefficient of variation, and strength coefficient of variation), and the detection indexes and methods were as follows: an Instron 1122 universal material testing machine was used: the four different fineness fibers subjected to different conditions were subjected to tensioning, environmental control was performed according to the requirements of the standard test method for reinforcing materials, the temperature was 23±2℃, and the relative humidity was (50±10)%. The tensioning speed was 250mm / min; the clamp was a rope test clamp produced by INSTRON Company, which could ensure that the sample did not slip during the testing process; the clamping distance was 500mm. The fiber was pulled to break, and the instrument automatically obtained the results. The average testing was performed 10 times per can, the average value was taken, the testing results were given by the software, and the testing results are shown in Table 1:

[0092] Table 1

[0093]

[0094] Example 2

[0095] The present example provides a polyamide spinning oil, and the content of each component is as follows:

[0096] Polyethylene glycol sorbitol hexaoleate 22 parts, polyethylene glycol 15-hydroxystearate 18 parts, triethanolamine di(octadecanoate) 18 parts, alkyl phenol polyoxyethylene quaternary ammonium salt 6 parts, chitosan quaternary ammonium salt 6 parts, tri glycerol monostearate 28 parts, 2(3)-tert-butyl-4-hydroxyanisole 8 parts, anti-phenolic yellowing agent APY 3 parts, penetrant JFC 4 parts, and bis(2,6-diisopropylphenyl) carbodiimide 3 parts.

[0097] The preparation method of the polyamide spinning oil of the present example is the same as that of Example 1.

[0098] The present example also provides a polyamide fiber, which is made of the polyamide spinning oil of the present example, and the preparation method is the same as that of Example 1.

[0099] The polyamide fiber of the present example was subjected to performance testing (breaking strength, breaking elongation, modulus of elasticity, elongation coefficient of variation, and strength coefficient of variation), and the detection indexes and methods were the same as those of Example 1; the testing results are shown in Table 2:

[0100] Table 2

[0101]

[0102] Comparative Example 1

[0103] The present comparative example provides a polyamide fiber, which is not subjected to the infiltration treatment of the spinning oil during the preparation process, and is directly hot-drawn and wound.

[0104] The polyamide fiber of the present comparative example was subjected to performance tests (breaking strength, elongation at break, modulus of elasticity, coefficient of variation of elongation, and coefficient of variation of strength), and the test indexes and methods were the same as those of Example 1. The test results are shown in Table 3.

[0105] Table 3

[0106]

[0107] Comparative Example 2

[0108] The present comparative example provides a polyamide fiber, which is subjected to an immersion treatment using a commercially available spin finish AZ-60 (Sanyo Chemical Industries, Ltd.) during its preparation process, direct heat drawing, and winding.

[0109] The polyamide fiber of the present comparative example was subjected to performance tests (breaking strength, elongation at break, modulus of elasticity, coefficient of variation of elongation, and coefficient of variation of strength), and the test indexes and methods were the same as those of Example 1. The test results are shown in Table 4.

[0110] Table 4

[0111]

[0112]

[0113] Comparative Example 3

[0114] Test Example

[0115] The fiber samples of Example 1, Example 2, Comparative Example 1, and Comparative Example 2, which have a spinning draw speed of 2000 m / min, were subjected to comparative performance tests.

[0116] Antibacterial performance test: The fibers were dispersed in a suspension containing Staphylococcus aureus ATCC 6538, and then incubated at 37°C for 12 h, respectively. The optical density of the bacteria at 600 nm (OD600) was measured every 2 h by ultraviolet-visible spectroscopy, and the bactericidal rate of each fiber on Staphylococcus aureus was calculated.

[0117] Antioxidant performance test: 7 mmol / L of an ABTS aqueous solution was mixed with an equal volume of a 2.45 mmol / L aqueous solution of potassium persulfate, and after 16 h of reaction at room temperature in the dark, an ABTS working mother liquor was obtained. When used, the ABTS working mother liquor was diluted to an appropriate concentration so that its absorbance value at 734 nm was 0.700 ± 0.025. Under the same experimental conditions, the polyamide fibers prepared in the above examples and comparative examples were immersed in the test solution, and then tested. Each sample was tested in parallel 5 times, and the average value was taken.

[0118] Antioxidant activity (%) = (D2 - D1) / D2 x 100%, wherein D2 is the initial absorbance value of the test solution, and D1 is the absorbance value after the test solution is immersed in the fiber for 30 min.

[0119] The hydrolysis resistance test method is as follows: the fiber sample is placed in a container containing a mixture of ethylene glycol and water (1:1, by volume) and boiled at 135°C under normal pressure for 120 h, after which the fiber sample is taken out and the mechanical strength test is carried out in a wet state, and the strength retention rate, i.e. the ratio of the strength after hydrolysis to the original strength, is calculated. The higher the mechanical property retention rate, the better the hydrolysis resistance of the fiber sample.

[0120] Mechanical property retention rate (%) = mechanical strength after boiling / initial mechanical strength x 100%.

[0121] The results are as follows:

[0122]

[0123] It can be seen that the polyamide fibers of Examples 1 and 2 produced using the oil agent of the present application have higher mechanical property indicators, including tensile breaking strength and initial modulus. Further, the polyamide fibers of Examples 1 and 2 based on the oil agent of the present application have better hydrolysis resistance, and the mechanical strength retention rate of the fibers after the hydrolysis experiment is higher, which is significantly higher than that of the fiber product without using the oil agent in Comparative Example 1 and the fiber product using the conventional oil agent in Comparative Example 2. At the same time, the polyamide fibers of Examples 1 and 2 based on the oil agent of the present application have good antioxidant activity and show stronger resistance to oxidative degradation. In addition, the polyamide fibers of Examples 1 and 2 based on the oil agent of the present application have obvious antibacterial effect, and the inhibition rate is more than 99%, which is significantly higher than that of the fiber product without using the oil agent in Comparative Example 1 and the fiber product using the conventional oil agent in Comparative Example 2.

[0124] The above describes and evaluates some embodiments of the present application. It should be understood that the present application is not limited to the above specific embodiments, and any person skilled in the art can make many possible changes and modifications to the technical solutions of the present application, or modify equivalent embodiments with equivalent changes, without departing from the scope of the technical solutions of the present application, which does not affect the essential content of the present application. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present application, without departing from the technical solutions of the present application, still belongs to the scope of protection of the technical solutions of the present application.

Claims

1. A polyamide spinning oil, characterized in that, By weight, it includes the following raw material components: 15-25 parts of polyethylene glycol sorbitan hexaoleate, 10-25 parts of polyethylene glycol 15-hydroxystearate, 10-20 parts of triethanolamine di(octadecanoate), 5-10 parts of alkylphenol polyoxyethylene quaternary ammonium salt, 5-10 parts of chitosan quaternary ammonium salt, 20-30 parts of triglyceride monostearate, 2-20 parts of 2(3)-tert-butyl-4-hydroxyanisole, 2-5 parts of anti-phenolic yellowing agent APY, 3-6 parts of penetrant JFC, and 1-5 parts of bis(2,6-diisopropylphenyl)carbodiimide.

2. The polyamide spinning oil agent according to claim 1, characterized in that, By weight, it includes the following raw material components: 20 parts of polyethylene glycol sorbitan hexaoleate, 20 parts of polyethylene glycol 15-hydroxystearate, 15 parts of triethanolamine di(octadecanoate), 7 parts of alkylphenol polyoxyethylene quaternary ammonium salt, 7 parts of chitosan quaternary ammonium salt, 25 parts of triglyceride monostearate, 7 parts of 2(3)-tert-butyl-4-hydroxyanisole, 4 parts of anti-phenolic yellowing agent APY, 5 parts of penetrant JFC, and 2 parts of bis(2,6-diisopropylphenyl)carbodiimide.

3. The method for preparing the polyamide spinning oil according to claim 1 or 2, characterized in that, Includes the following steps: S1. Polyethylene glycol sorbitan hexaoleate and polyethylene glycol 15-hydroxystearate are mixed in a certain proportion and stirred evenly to obtain mixture A; S2. Add triethanolamine di(octadecanoic acid) ester to mixture A obtained in step S1, stir until homogeneous, and obtain mixture B; S3. Add alkylphenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt to mixture B obtained in step S2 in sequence, and stir evenly to obtain mixture C; S4. Slowly add triglyceride monostearate to the mixture C obtained in step S3, and stir until homogeneous to obtain mixture D; S5. Add 2(3)-tert-butyl-4-hydroxyanisole and anti-phenolic yellowing agent APY to the mixture D obtained in step S4 in sequence, stir evenly, and then obtain mixture E. S6. Add penetrant JFC and bis(2,6-diisopropylphenyl)carbodiimide to the mixture E obtained in step S5, and stir evenly to obtain the polyamide spinning oil.

4. The preparation method according to claim 3, characterized in that, In step S1, the stirring conditions are: high-speed stirring at a constant temperature of 55-65℃ for 30-35 minutes, with a stirring speed of 800-850 rpm; And / or, in step S2, the stirring conditions are: stirring at a rate of 900-950 rpm for 20-25 minutes.

5. The preparation method according to claim 3, characterized in that, In step S3, the stirring conditions are as follows: stir at a speed of 1200-1250 rpm for 30-35 minutes; after the mixture C system becomes viscous, reduce the stirring speed to 850-900 rpm.

6. The preparation method according to claim 3, characterized in that, In step S4, the stirring conditions are as follows: stir at a speed of 500-1000 rpm for 30-35 minutes; then increase the speed to 1200-1250 rpm and continue stirring for 20-25 minutes.

7. The preparation method according to claim 3, characterized in that, In step S5, the stirring conditions are: stirring at a speed of 1500-1550 rpm for 30-35 minutes; And / or, in step S6, the stirring conditions are: stirring at a rate of 1500-1550 rpm for 40-45 min.

8. A polyamide fiber, characterized in that, It includes polyamide spinning oils prepared using the polyamide spinning oils described in claim 1 or 2 and the preparation methods described in any one of claims 3-7.

9. The polyamide fiber according to claim 8, characterized in that, The polyamide fiber has a fineness of 1 to 600 dtex; and / or a breaking strength of 3 to 10 cN / dtex, an elastic modulus of 10 to 50 cN / dtex, and an elongation at break of 20 to 50%.

10. A method for preparing polyamide fiber as described in claim 8, characterized in that, The process involves adding a polyamide spinning oil to the sizing tank of an oiling machine, immersing unsized synthetic fibers in the polyamide spinning oil, and passing them through the sizing tank of the oiling machine at a traction speed of 5–2000 m / min. After exiting the tank, the fibers are stretched at a high ratio and then wound up to obtain the polyamide fibers.

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