Polyamide spinning oil, preparation method thereof and polyamide fiber

Abstract

The invention belongs to the technical field of preparation of polyamide fibers, and particularly relates to polyamide spinning oil, a preparation method of the polyamide spinning oil and the polyamide fibers. The polyamide spinning oil is prepared from the following components in parts by weight, comprising the following raw material components: 15 to 25 parts of polyethylene glycol sorbitol hexoleate, 10 to 25 parts of polyethylene glycol 15-hydroxystearate, 10 to 20 parts of triethanolamine di (octadecanoic acid) ester, 5 to 10 parts of alkylphenol polyoxyethylene quaternary ammonium salt, 5 to 10 parts of chitosan quaternary ammonium salt, 20 to 30 parts of tripolyglycerol monostearate, 2 to 20 parts of 2 (3)-tert-butyl-4-hydroxy anisd, 2 to 5 parts of an anti-phenolic yellowing agent APY, 3 to 6 parts of a penetrant JFC and 2 to 5 parts of bis (2, 4-dihydroxy-4-hydroxyanisole. And 1 to 5 parts of 2, 6-diisopropyl phenyl) carbodiimide. According to the polyamide spinning oil, through reasonable design, the smoothness, flexibility, bundling property, antistatic property, yellowing resistance and other properties of polyamide spinning fibers are remarkably improved, meanwhile, the polyamide spinning oil has the synergistic effects of resisting bacteria, resisting oxidative degradation and resisting hydrolysis, and finally the product performance of the polyamide fibers is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of polyamide fiber preparation, and particularly relates to a polyamide spinning oil agent and a preparation method thereof, and polyamide fiber. Background Art

[0002] Polyamide fiber is an important type of synthetic fiber, also widely known as nylon. The main raw material of polyamide fiber is polyamide, and the molecular structure of this polymer contains repeated amide groups. These amide groups make nylon fiber have excellent strength, wear resistance, flexibility and chemical corrosion resistance. Its excellent performance and wide application prospects 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. 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 purpose of using oil mainly includes the following points: (1) Lubrication: During 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. The oil can form a lubricating film on the surface of the fiber and the equipment, reduce friction, improve the smoothness and flexibility of the fiber, and make the fiber pass smoothly through the spinning machine, thereby reducing broken fibers and improving production efficiency. (2) Prevent static electricity: During the spinning process, static electricity is easily generated when the fiber contacts the equipment. Static electricity can cause attraction between fibers and adsorption between fibers and the surface of the equipment, resulting in fiber agglomeration, reduced spinning quality, and even sparks, causing safety hazards. Adding antistatic agents to oils can effectively reduce the generation and impact of static electricity, improve the bundling of fibers, and ensure smooth spinning of fibers. (3) Reduce fiber breakage: During the spinning process, the fiber may be subjected to forces such as stretching and extrusion, and may easily break. The use of oil can improve the softness and ductility of the fiber, reduce fiber breakage when subjected to force, and increase the success rate of spinning. (4) Protect equipment: The parts of spinning equipment are prone to wear and tear after long-term high-speed operation. The oil can form a protective film to reduce equipment wear and corrosion and extend the service life of the equipment. (5) Adjust fiber properties: The oil can adjust the physical properties of the fiber such as surface tension and surface energy, thereby affecting the fiber's hygroscopicity, softness, glossiness and other characteristics, so that the final product has better quality and performance.

[0004] But in addition to this, polyamide fibers are easily oxidized and yellowed during the processing and molding process, and polyamide fibers are also easy to absorb water and the amide bonds are easily hydrolyzed. In addition, polyamide fibers are also easy to breed bacteria and be contaminated by bacteria. In summary, it is necessary to develop a product that not only has the properties of conventional oils, but also has antibacterial, antioxidant, and hydrolysis-resistant properties.

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

[0006] Chinese patent CN103422342A provides a polyamide fiber oil, characterized in that the polyamide fiber oil is mixed with the following components in percentage based on the total weight of the polyamide fiber oil: 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 of the patent has appropriate smoothness and high antistatic performance, and has good application prospects, but it is not designed for antibacterial, antioxidant, hydrolysis resistance and other properties.

[0007] Chinese patent CN115897216A provides a degradable oil for nylon high temperature resistant and anti-yellowing spinning and its preparation method, including 1-2 parts of coated composite nano-aerogel, 5-10 parts of zinc chloride solution, 0.5-1.2 parts of hexadecyltrimethylammonium 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 sizing agent, 1-2 parts of defoamer, and 0.8-1.5 parts of polyether silicone oil. The oil in this patent has good degradation performance, but it also does not introduce antibacterial, antioxidant, hydrolysis resistance and other designs.

[0008] In view of this, the present invention is proposed. Summary of the invention

[0009] The purpose of the present invention is to provide a polyamide spinning oil, a preparation method thereof and polyamide fiber; the polyamide spinning oil significantly improves the smoothness and flexibility, bundling, antistatic, yellowing resistance and other properties of the polyamide spinning fiber through reasonable design, and also has the synergistic effects of antibacterial, anti-oxidative degradation and hydrolysis resistance, ultimately improving the product performance and stability of the polyamide fiber, thereby effectively solving a series of problems of the polyamide fiber in the spinning process.

[0010] In order to achieve the above object, the present invention provides the following technical solutions:

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

[0012] 15-25 parts of polyethylene glycol sorbitan hexaoleate, 10-25 parts of polyethylene glycol 15-hydroxystearate, 10-20 parts of triethanolamine dioctadecanoate, 5-10 parts of alkylphenol polyoxyethylene quaternary ammonium salt, 5-10 parts of chitosan quaternary ammonium salt, 20-30 parts of triglycerol monostearate, 2-20 parts of 2(3)-tert-butyl-4-hydroxyanisole, 2-5 parts of anti-phenol yellowing agent APY, 3-6 parts of penetrant JFC and 1-5 parts of bis(2,6-diisopropylphenyl)carbodiimide.

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

[0014] 20 parts of polyethylene glycol sorbitan hexaoleate, 20 parts of polyethylene glycol 15-hydroxystearate, 15 parts of triethanolamine dioctadecanoate, 7 parts of alkylphenol polyoxyethylene quaternary ammonium salt, 7 parts of chitosan quaternary ammonium salt, 25 parts of triglycerol monostearate, 7 parts of 2(3)-tert-butyl-4-hydroxyanisole, 4 parts of anti-phenol yellowing agent APY, 5 parts of penetrant JFC and 2 parts of bis(2,6-diisopropylphenyl)carbodiimide.

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

[0016] S1, mixing polyethylene glycol sorbitol hexaoleate and polyethylene glycol 15-hydroxystearate in proportion, stirring evenly to obtain a mixture A;

[0017] S2, adding triethanolamine dioctadecanoate to the mixture A obtained in step S1, stirring evenly to obtain a mixture B;

[0018] S3, adding alkylphenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt to the mixture B obtained in step S2 in sequence, stirring evenly to obtain a mixture C;

[0019] S4, slowly adding tripolyglycerol monostearate to the mixture C obtained in step S3, and stirring evenly to obtain a mixture D;

[0020] S5, adding 2(3)-tert-butyl-4-hydroxyanisole and anti-phenol yellowing agent APY to the mixture D obtained in step S4 in sequence, stirring evenly to obtain a mixture E;

[0021] 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.

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

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

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

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

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

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

[0028] On the other hand, a polyamide fiber is provided, characterized in that it is made of the polyamide spinning oil described above and the polyamide spinning oil prepared by any of the preparation methods described above.

[0029] In an optional embodiment, 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%.

[0030] In another aspect, a method for preparing the polyamide fiber as described above is provided, comprising adding the polyamide spinning oil into the sizing tank of an oiling machine, then immersing the unsized synthetic fiber into the polyamide spinning oil, and passing the fiber through the sizing tank of the oiling machine at a pulling speed of 5 to 2000 m / min, and winding the fiber after exiting the tank after high-multiple stretching to obtain the polyamide fiber.

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

[0032] (1) The polyamide spinning oil of the present invention significantly improves the smoothness, flexibility, bundling, antistatic, yellowing resistance and other properties of polyamide spinning fibers through reasonable design. It also has the synergistic effects of antibacterial, anti-oxidative degradation and hydrolysis resistance, rather than mechanical accumulation acting alone, and ultimately improves the product performance and stability of the polyamide fiber, thereby effectively solving a series of problems of the polyamide fiber in the spinning process, and plays a vital role in the stability of the fiber spinning process, the improvement of fiber quality and the improvement of production efficiency. It can not only ensure the smooth progress of the spinning process and improve the quality and performance of the product, but also improve production efficiency, reduce production costs and promote the sustainable development of the enterprise.

[0033] (2) The polyamide spinning oil of the present invention ensures uniform oiling and reduces splashing during use, and is suitable for smooth high-speed spinning production; it has good spinnability, effectively improves fiber quality, and makes the first-class fiber quality rate as high as 97% or more, significantly improving the fiber quality and production efficiency. It also makes the winding and unwinding process smoother; it meets the requirements of unwinding, stretching, winding and false twisting in the fiber processing process, maintains the uniformity of false twisting tension, thereby ensuring the stability of the spinning process, reducing fiber lint and broken ends, and no oil impurities are deposited on the post-spinning equipment and no masterbatch pigment precipitation occurs.

[0034] (3) The wetting time of the spinning oil of the present invention on the polyamide fiber is 0.5 to 10 seconds, and the surface tension is 2 to 40 N / m. It has excellent lubrication performance, excellent adsorption performance and good aggregation performance, and effectively reduces the white powder generated by friction during the production of nylon yarn; in addition, the viscosity of the oil is less affected by temperature, and it is not easy to produce oil smoke after heating, and there is less coking on the surface of the heating roller, which is easy to clean. The polyamide fiber prepared by using the oil of the present invention has good bundling, stretching and molding, the filament bundle is bright, the oil odor is small, 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 invention clearer, the technical scheme in the embodiment of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention. The process parameters of the following embodiments that do not specify specific conditions are usually based on conventional conditions.

[0036] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in the present invention.

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

[0038] 15-25 parts of polyethylene glycol sorbitan hexaoleate (e.g. 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts), 10-25 parts of polyethylene glycol 15-hydroxystearate (e.g. 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), 10-20 parts of triethanolamine dioctadecanoate (e.g. 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), triglycerol 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-phenol yellowing agent APY 2 to 5 parts (such as 2 parts, 3 parts, 4 parts, 5 parts), penetrant JFC 3 to 6 parts (such as 3 parts, 4 parts, 5 parts, 6 parts) and bis(2,6-diisopropylphenyl)carbodiimide 1 to 5 parts (such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts).

[0039] During the processing and molding process, polyamide fibers are susceptible to oxidation and yellowing. This is mainly because polyamide fibers are easily oxidized by oxygen in a high temperature and high humidity environment, resulting in the breaking of chemical bonds in the polyamide molecular structure and the generation of products containing phenolic groups, which causes the fiber surface to yellow. Polyamide fibers also have the characteristics of easy water absorption and easy hydrolysis of amide bonds. This is because their molecular structure contains a large number of polar amide groups (-CONH-), which can form hydrogen bonds with water molecules. Therefore, during the processing and molding process, polyamide fibers easily absorb moisture from the surrounding environment, causing the fibers to swell and even hydrolyze, affecting their physical properties and dimensional stability. The amide bonds (-CONH-) in polyamide molecules are susceptible to hydrolysis, especially in a high temperature and high humidity environment. Hydrolysis can cause the polyamide molecular chain to break, reduce the molecular weight and mechanical properties of the fiber, and even cause the fiber to be destroyed. Polyamide fibers are prone to bacterial growth. The problem of bacterial contamination mainly comes from the following aspects: (1) Water absorption: Polyamide fibers have strong water absorption, which makes the fiber surface moist and provides a moist environment for bacterial growth. Bacteria usually need water to grow and reproduce, so the water absorption of the fiber surface increases the possibility of bacterial growth. (2) Surface morphology: The microscopic morphology of the polyamide fiber surface may also promote bacterial attachment and growth. For example, the tiny bumps on the fiber surface or the gaps between fibers can provide tiny spaces for bacterial growth.

[0040] In view of the above reasons, the inventor has successfully developed a novel antibacterial, oxidation-resistant and hydrolysis-resistant polyamide spinning oil by rationally designing the oil formulation, including smoothing softener, additives with synergistic properties such as antibacterial, antistatic and antioxidant, one or more of oxidation-resistant, yellowing-resistant and hydrolysis-resistant polyamide spinning oil. In the polyamide spinning oil formulation of the present invention, polyethylene glycol sorbitol hexaoleate is used as a smoothing agent, polyethylene glycol 15-hydroxystearate is used as a softener, triethanolamine di(octadecanoic acid) ester is used as a clustering agent, and tripolyglycerol monostearate is used as a surfactant; wherein, the organic combination of alkylphenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt exhibits antistatic and antibacterial synergistic effects. These two substances each have certain antibacterial and antistatic properties, but they can enhance each other after combination to produce a stronger comprehensive effect. Specifically, alkylphenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt are both cationic surfactants, which have the ability to form a protective film on the fiber surface, and these protective films can effectively block the generation and accumulation of static electricity, thereby reducing the static electricity charging phenomenon of fiber materials. Alkylphenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt also have good antibacterial activity, can inhibit and kill microorganisms such as bacteria and fungi, and they can block the growth and reproduction of microorganisms by destroying the cell wall or cell membrane of microorganisms, thereby achieving an antibacterial effect. Synergistic effect is as follows: after alkylphenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt are organically combined, their antibacterial and antistatic effects can be enhanced mutually. This is because they may form a more stable and uniform protective film on the surface, while increasing the density of cations, making the inhibitory effect of static electricity and microorganisms more significant. Therefore, the organic combination of alkylphenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt not only provides the dual functions of antistatic and antibacterial, but also enhances their comprehensive performance through synergistic effect, providing an effective solution for the antistatic and antibacterial products in the application fields such as fiber materials.

[0041] In particular, 2(3)-tert-butyl-4-hydroxyanisole, as a fat-soluble antioxidant, has good thermal stability and is helpful in reducing the oxidative degradation of fibers during production and subsequent use. Tert-butyl-4-hydroxyanisole has strong antioxidant and antibacterial abilities and can inhibit the growth of Staphylococcus aureus and aflatoxin. Alkylphenol polyoxyethylene quaternary ammonium salts and chitosan quaternary ammonium salts have good antibacterial activity and can inhibit and kill microorganisms such as bacteria and fungi. Therefore, these two substances have a synergistic antibacterial effect and achieve an organic combination of antibacterial and antioxidant properties. 2(3)-tert-butyl-4-hydroxyanisole is a lipophilic compound that has antibacterial activity against molds and Gram-positive bacteria. It also has an antioxidant effect: 2(3)-tert-butyl-4-hydroxyanisole, as an antioxidant, can effectively prevent fiber raw materials from being affected by oxidation during the spinning process. Adding 2(3)-tert-butyl-4-hydroxyanisole can stabilize the active groups in polyamide fiber raw materials, inhibit the occurrence of oxidation reactions, and extend the service life of the fiber. During the spinning process, fiber raw materials are easily affected by factors such as oxygen, light, and heat in the external environment and oxidized, thereby affecting the quality and performance of the fiber. By adding antioxidants such as 2(3)-tert-butyl-4-hydroxyanisole, the quality of the fiber raw materials can be effectively protected, preventing them from being damaged by oxidation during the spinning process, and improving the quality and yield of the fiber. Improving product stability: 2(3)-tert-butyl-4-hydroxyanisole, as an antioxidant, can improve the stability of fiber spinning oils. During the spinning process, the influence of oxidation may cause the performance of the spinning oil to decline, thereby affecting the processing quality of the fiber. By adding antioxidants, such as 2(3)-tert-butyl-4-hydroxyanisole, the performance stability of the spinning oil can be effectively maintained, ensuring the smooth progress of the fiber processing process.

[0042] In particular, bis(2,6-diisopropylphenyl)carbodiimide (DCDPA) plays an important role as a hydrolysis resistance agent in the oil. The bis(2,6-diisopropylphenyl)carbodiimide in the oil can form a protective film on the surface of the fiber material, blocking the penetration of water and oxygen, reducing the contact between the fiber molecular chain and water molecules, and thus slowing down the occurrence of hydrolysis reactions. It can also competitively adsorb with water molecules, reduce the diffusion and penetration of water molecules inside the fiber material, and thus reduce the rate of hydrolysis reactions. It can also stabilize the fiber structure and reduce the sensitivity of hydrolysis reactions by chemically reacting with active groups such as hydroxyl groups in polyamide fiber materials. It is mainly reflected in the following aspects. Preventing hydrolysis reactions: In fiber oils, DCDPA can inhibit the hydrolysis of fibers and other organic substances. The components in fiber oils are often affected by moisture and other conditions in the environment and undergo hydrolysis reactions, resulting in a decrease in the performance of the fiber oils. DCDPA can slow down or prevent the occurrence of these hydrolysis reactions, thereby improving the stability and durability of the fiber oils. 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 competitively adsorb with water molecules, reducing the diffusion and penetration of water molecules inside fiber materials, thereby reducing the rate of hydrolysis reactions. It can also stabilize the fiber structure and reduce the sensitivity of hydrolysis reactions by chemically reacting with active groups such as hydroxyl groups in fiber materials. Enhance the performance of oils: DCDPA as a hydrolysis-resistant agent can also enhance the performance of fiber oils, allowing them to maintain good effects in humid or high temperature environments. By reducing the occurrence of hydrolysis reactions, DCDPA helps maintain the viscosity, lubricity and antioxidant properties of fiber oils and prolongs their service life. Improve processing efficiency: Fiber oils play a role in lubricating and protecting fibers during textile processing, and DCDPA as a hydrolysis-resistant agent can ensure that fiber oils are stable during processing and are not easily affected by hydrolysis, thereby improving processing efficiency and product quality. Improve fiber properties: The use of DCDPA improves the hydrolysis resistance of the fiber itself, and can also improve the softness, glossiness and wear resistance of the fiber, so that the fiber products have better feel and appearance. As a hydrolysis resistance agent in fiber oil, bis(2,6-diisopropylphenyl)carbodiimide plays an important role in the stability, performance and processing efficiency of fiber oil, and helps to improve the quality and service life of fiber products.

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

[0044] The role of APY in fiber oil mainly includes the following aspects: APY can effectively block the free amino groups on polyamide fibers and prevent fibers from absorbing nitrophenol derivatives of butylated hydroxytoluene. APY can effectively prevent or slow down the oxidation reaction between fiber raw materials and oxygen, protect fiber raw materials from oxidative damage, improve the durability and stability of fibers, and extend the service life of fibers. Since fibers are easily affected by external environmental factors such as light and oxygen, they will undergo yellowing reactions, resulting in changes in the color of fibers. APY can inhibit or slow down the occurrence of such yellowing reactions, 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 fiber oils, extend the effective service life of the oils, and ensure their stability and performance during processing. APY can reduce the content of phenolic substances, reduce the frequency of equipment cleaning, and improve the stability and processing efficiency of the production line. The anti-phenolic yellowing agent APY helps to reduce the content of phenolic substances caused by oxidation in fiber raw materials and fiber products, reduce the occurrence of oxidation reactions, and thus improve 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 anti-oxidation, yellowing prevention, fiber oil stabilization, processing efficiency improvement and fiber quality improvement, and is an important functional additive.

[0045] The weight parts of the present invention mainly include the disclosed numerical range, any numerical value (including integer and decimal) or any interval of two numerical values ​​in the disclosed range, or multiple discontinuous intervals, and also include numerical values ​​or numerical ranges close to the end value of the numerical range whose effects can be expected to be similar, such as 5-10 parts, not only including 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts and any interval of two parts, for other numerical ranges, not exemplified one by one, all are included in the present invention. Therefore, the present invention also includes the sub-range of any numerical range that has been directly disclosed or any specific numerical value therein.

[0046] In order to further optimize the therapeutic effect of the polyamide spinning oil, the present invention studies the influence of different proportions of various raw material components on the effect, and obtains better raw material component proportions, namely, 20 parts of polyethylene glycol sorbitan hexaoleate, 20 parts of polyethylene glycol 15-hydroxystearate, 15 parts of triethanolamine dioctadecanoate, 7 parts of alkylphenol polyoxyethylene quaternary ammonium salt, 7 parts of chitosan quaternary ammonium salt, 25 parts of triglycerol monostearate, 7 parts of 2(3)-tert-butyl-4-hydroxyanisole, 4 parts of anti-phenol yellowing agent APY, 5 parts of penetrant JFC and 2 parts of bis(2,6-diisopropylphenyl)carbodiimide.

[0047] The polyamide spinning oil of the present invention can be used directly or prepared into an emulsion with water. When the emulsion is prepared, the concentration of the emulsion is 10±2%. The water used for preparation is soft water, the hardness of which is less than 1pg / g, and the pH value is 6.5-7.5. The measured components are slowly added into the soft water according to the emulsion concentration requirements, and the oil can be used after high-speed stirring or ultrasonic treatment for 5-60 minutes at 20-60°C. The stirring speed is 1500-3000rpm, or the ultrasonic power is 100-300W.

[0048] According to a second aspect of the present invention, there is provided a method for preparing the above-mentioned polyamide spinning oil, comprising the following steps:

[0049] S1, mixing polyethylene glycol sorbitol hexaoleate and polyethylene glycol 15-hydroxystearate in proportion, stirring evenly to obtain a mixture A;

[0050] S2, adding triethanolamine dioctadecanoate to the mixture A obtained in step S1, stirring evenly to obtain a mixture B;

[0051] S3, adding alkylphenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt to the mixture B obtained in step S2 in sequence, stirring evenly to obtain a mixture C;

[0052] S4, slowly adding tripolyglycerol monostearate to the mixture C obtained in step S3, and stirring evenly to obtain a mixture D;

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

[0054] 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.

[0055] In the above preparation method, as a preferred embodiment, in step S1, the stirring process conditions are: high-speed stirring at a constant temperature of 55 to 65° C. for 30 to 35 minutes, and a stirring rate of 800 to 850 rpm;

[0056] Optionally, in step S2, the stirring process conditions are: stirring at a rate of 900 to 950 rpm for 20 to 25 min;

[0057] Optionally, in step S3, the stirring process conditions are: stirring at a rate of 1200 to 1250 rpm for 30 to 35 minutes; after the mixture C system becomes viscous, the stirring rate is reduced to 850 to 900 rpm;

[0058] Optionally, in step S4, the stirring process conditions are: stirring at a speed of 500 to 1000 rpm for 30 to 35 minutes; then increasing the speed to 1200 to 1250 rpm, and continuing stirring for 20 to 25 minutes;

[0059] Optionally, in step S5, the stirring process conditions are: stirring at a rate of 1500 to 1550 rpm for 30 to 35 minutes;

[0060] Optionally, in step S6, the stirring process conditions are: stirring at a rate of 1500-1550 rpm for 40-45 min.

[0061] According to a third aspect of the present invention, there is provided a polyamide fiber, comprising the polyamide spinning oil as described above and the polyamide spinning oil obtained by the preparation method as described above.

[0062] In the above-mentioned polyamide fiber, as a preferred embodiment, the fineness of the polyamide fiber is 1 to 600 dtex. For example, the fineness of the polyamide fiber can be 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.; the breaking strength is 3 to 10 cN / dtex. For example, the breaking strength is 3 cN / dtex, 6 cN / dtex, 8 cN / dtex, 9 cN / dtex or 10 cN / dtex, etc. The elastic modulus is 10 to 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 N / dtex or 50 N / dtex. The elongation at break is 20 to 50%. The strength of polyamide fibers made from conventional oils is generally 2 to 6 cN / dtex, and the modulus is generally 20 to 30 cN / dtex. The various properties of the polyamide fibers provided in the embodiments of the present invention are superior to the various properties of polyamide fibers in the prior art.

[0063] According to a fourth aspect of the present invention, there is provided a method for preparing the polyamide fiber as described above, which is characterized in that it comprises adding a polyamide spinning oil into a sizing tank of an oiling machine, then immersing unsized synthetic fibers into the polyamide spinning oil, and passing the fibers through the sizing tank of the oiling machine at a pulling speed of 5 m / min-2000 m / min, and winding the fibers after exiting the tank after high-multiple stretching to obtain the polyamide fibers.

[0064] The present invention will be described in detail below in conjunction with embodiments of the present invention, and each example is provided by way of explanation of the present invention without limiting the present invention. In fact, it will be clear to those skilled in the art that modifications and variations may be made in the present invention without departing from the scope or spirit of the present invention. For example, a feature shown or described as a part of an embodiment may be used in another embodiment to produce yet another embodiment. Therefore, it is desired that the present invention includes such modifications and variations within the scope of the appended claims and their equivalents.

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

[0066] In the following embodiments,

[0067] Polyethylene glycol sorbitan hexaoleate was purchased from Sigma Aldrich Reagent Company with the brand number 466409.

[0068] Polyethylene glycol 15-hydroxystearate was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., brand number K487242.

[0069] Triethanolamine dioctadecanoate was purchased from Xi'an Qiyue Biological Company, brand number Q-0175039.

[0070] Alkylphenol polyoxyethylene quaternary ammonium salt was purchased from West Asia Reagents with the brand name A16677.

[0071] Chitosan quaternary ammonium salt was purchased from Roan Reagent Co., Ltd., brand R140174.

[0072] Triglycerol monostearate was purchased from Roan Reagent Co., Ltd. with the brand number R121821.

[0073] 2(3)-tert-Butyl-4-hydroxyanisole was purchased from Shanghai MacLean Reagent Company with the brand number B802177.

[0074] The anti-phenol yellowing agent APY was purchased from Guangzhou Ruiqi Chemical Technology Co., Ltd., and the brand name is RICHFIX APY.

[0075] The penetrant JFC was purchased from Guangdong Runhong Chemical Company with the brand name JFC-1.

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

[0077] AZ-60 oil, produced by Sanyo Company of Japan, the brand name is AZ-60.

[0078] ABTS (2,2'-azino-bis(3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt) was purchased from Sinopharm Chemical Reagent Co., Ltd. with the brand name TMLT18908G1.

[0079] Potassium persulfate was purchased from Sinopharm Chemical Reagent Co., Ltd. with the brand number 10017428.

[0080] Example 1

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

[0082] 20 parts of polyethylene glycol sorbitan hexaoleate, 20 parts of polyethylene glycol 15-hydroxystearate, 15 parts of triethanolamine dioctadecanoate, 7 parts of alkylphenol polyoxyethylene quaternary ammonium salt, 7 parts of chitosan quaternary ammonium salt, 25 parts of triglycerol monostearate, 7 parts of 2(3)-tert-butyl-4-hydroxyanisole, 4 parts of anti-phenol yellowing agent APY, 5 parts of penetrant JFC and 2 parts of bis(2,6-diisopropylphenyl)carbodiimide.

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

[0084] S1: adding polyethylene glycol sorbitan hexaoleate and polyethylene glycol 15-hydroxystearate into a stirrer, stirring at a constant temperature of 60° C. for 30 minutes at a rotation speed of 800 rpm to obtain a mixture 1;

[0085] S2: adding triethanolamine dioctadecanoate to the mixture 1 in step S1, and stirring at a rotation speed of 900 rpm for 20 minutes to obtain a mixture 2;

[0086] S3: adding alkylphenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt to the mixture 2 in step S2, stirring at 1200 rpm for 30 minutes to obtain a mixture 3. When the mixture 3 system becomes viscous, reducing the stirring speed to 900 rpm;

[0087] S4: Triglycerol monostearate is slowly added to the mixture 3 described in the above 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: Add 2(3)-tert-butyl-4-hydroxyanisole and anti-phenol yellowing agent APY to the mixture 4 in step S4, and stir at 1500 rpm for 30 minutes to obtain a mixture 5;

[0089] S6: Add penetrant JFC and bis(2,6-diisopropylphenyl)carbodiimide to the mixture 5 in step S5, and stir at a rotation speed of 1500 rpm for 40 minutes to obtain a spinning oil.

[0090] The present embodiment also provides a polyamide fiber, which is made using the polyamide spinning oil of the present embodiment. The preparation method is as follows: the polyamide spinning oil is added to the sizing tank of an oiling machine, and then the unsized synthetic fiber is immersed in the polyamide spinning oil, and the fiber is pulled through the sizing tank of the oiling machine at a pulling speed of 2000m / min, 1600m / mim, 1400m / min, and 1200m / min. After exiting the tank, the fiber is stretched at a high multiple and then rolled up to obtain the polyamide fiber.

[0091] The polyamide fiber of this embodiment was subjected to performance tests (breaking strength, breaking elongation, elastic modulus, elongation variation coefficient and strength variation coefficient), and the detection indicators and methods were as follows: Using Instron 1122 universal material testing machine: the four fibers with different deniers that had been subjected to different conditions were stretched, and the environment was controlled according to the requirements of the test method standard for reinforcing materials, with a temperature of 23±2°C and a relative humidity of (50±10)%. The stretching speed was 250 mm / min; the clamp was a rope test clamp produced by INSTRON, which could ensure that the sample did not slip during the test; the clamping spacing was 500 mm. Stretch until the fiber breaks, and the instrument automatically obtains the result. Each reel of silk was tested 10 times on average, and the average value was taken. The test results were given by the software, and the test results are shown in Table 1:

[0092] Table 1

[0093]

[0094] Example 2

[0095] This embodiment provides a polyamide spinning oil, and the content of each component is as follows:

[0096] 22 parts of polyethylene glycol sorbitan hexaoleate, 18 parts of polyethylene glycol 15-hydroxystearate, 18 parts of triethanolamine dioctadecanoate, 6 parts of alkylphenol polyoxyethylene quaternary ammonium salt, 6 parts of chitosan quaternary ammonium salt, 28 parts of triglycerol monostearate, 8 parts of 2(3)-tert-butyl-4-hydroxyanisole, 3 parts of anti-phenol yellowing agent APY, 4 parts of penetrant JFC and 3 parts of bis(2,6-diisopropylphenyl)carbodiimide.

[0097] The preparation method of the polyamide spinning oil in this embodiment is the same as that in Example 1.

[0098] This embodiment also provides a polyamide fiber, which is made using the polyamide spinning oil of this embodiment, and the preparation method is the same as that of Example 1.

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

[0100] Table 2

[0101]

[0102] Comparative Example 1

[0103] This comparative example provides a polyamide fiber, which is not impregnated with a spinning oil during its preparation process and is directly hot-drawn and wound.

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

[0105] Table 3

[0106]

[0107] Comparative Example 2

[0108] This comparative example provides a polyamide fiber, which is prepared by using a commercially available spinning oil AZ-60 (Sanyo Co., Ltd., Japan) for impregnation treatment, direct hot drawing and winding.

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

[0110] Table 4

[0111]

[0112]

[0113] Comparative Example 3

[0114] Test Case

[0115] Relevant performance tests and comparisons were performed on the fiber samples of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 with a spinning and drawing speed of 2000 m / min.

[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. The optical density of the bacteria at 600 nm (OD600) was measured every 2 h using UV-visible spectroscopy, and the bactericidal rate of each fiber against Staphylococcus aureus was calculated.

[0117] Antioxidant performance test: 7mmol / L ABTS aqueous solution and 2.45mmol / L potassium persulfate aqueous solution were mixed in equal volumes, and reacted in the dark at room temperature for 16 hours to obtain ABTS working stock solution. When used, the ABTS working stock solution was diluted to an appropriate concentration so that its absorbance at 734nm was 0.700±0.025. Under the same experimental conditions, the polyamide fibers prepared in the above embodiments and comparative examples were immersed in the test solution and tested. Each sample was tested 5 times in parallel and the average value was taken.

[0118] Antioxidant activity (%) = (D2-D1) / D2×100%, where 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 minutes.

[0119] The test method for hydrolysis resistance is as follows: put the fiber sample into a container containing a mixture of ethylene glycol and water (1:1, volume ratio), boil it continuously at 135°C under normal pressure for 120 hours, then take out the fiber sample, perform a mechanical strength test in a wet state, and calculate the strength retention rate, that is, the ratio of the strength after hydrolysis to the strength in the original state. A high mechanical property retention rate indicates that the fiber sample has good hydrolysis resistance.

[0120] Mechanical property retention rate (%) = mechanical strength after boiling / initial mechanical strength × 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 of the present invention have higher mechanical performance indicators, including tensile strength at break and initial modulus. Furthermore, the polyamide fibers of Examples 1 and 2 based on the oil of the present invention have better hydrolysis resistance, and the mechanical strength retention rate of the fibers after the hydrolysis experiment is higher, which is significantly higher than the fiber product without oil in Comparative Example 1 and the fiber product with conventional oil in Comparative Example 2. At the same time, the polyamide fibers of Examples 1 and 2 based on the oil of the present invention 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 of the present invention have obvious antibacterial effects, with an antibacterial rate of more than 99%, which is significantly higher than the fiber product without oil in Comparative Example 1 and the fiber product with conventional oil in Comparative Example 2.

[0124] The above describes and evaluates the efficacy of some embodiments of the present invention. It should be understood that the present invention is not limited to the above specific implementations. Any technician familiar with the art can use the above disclosed methods and technical contents to make many possible changes and modifications to the technical solutions of the present invention without departing from the scope of the technical solutions of the present invention, or modify them into equivalent embodiments of equivalent changes, which does not affect the essential content of the present invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solutions of the present invention still falls within the scope of protection of the technical solutions of the present invention.

Claims

1. A polyamide spinning oil, characterized in that: The raw material components are as follows: 15-25 parts of polyethylene glycol sorbitan hexaoleate, 10-25 parts of polyethylene glycol 15-hydroxystearate, 10-20 parts of triethanolamine dioctadecanoate, 5-10 parts of alkylphenol polyoxyethylene quaternary ammonium salt, 5-10 parts of chitosan quaternary ammonium salt, 20-30 parts of triglycerol monostearate, 2-20 parts of 2(3)-tert-butyl-4-hydroxyanisole, 2-5 parts of anti-phenol yellowing agent APY, 3-6 parts of penetrant JFC and 1-5 parts of bis(2,6-diisopropylphenyl)carbodiimide.

2. The polyamide spinning oil according to claim 1, characterized in that The raw material components are as follows: 20 parts of polyethylene glycol sorbitan hexaoleate, 20 parts of polyethylene glycol 15-hydroxystearate, 15 parts of triethanolamine dioctadecanoate, 7 parts of alkylphenol polyoxyethylene quaternary ammonium salt, 7 parts of chitosan quaternary ammonium salt, 25 parts of triglycerol monostearate, 7 parts of 2(3)-tert-butyl-4-hydroxyanisole, 4 parts of anti-phenol yellowing agent APY, 5 parts of penetrant JFC and 2 parts of bis(2,6-diisopropylphenyl)carbodiimide.

3. The method for preparing a polyamide spinning oil according to claim 1 or 2, characterized in that: The following steps are involved: S1, mixing polyethylene glycol sorbitol hexaoleate and polyethylene glycol 15-hydroxystearate in proportion, stirring evenly to obtain a mixture A; S2, adding triethanolamine dioctadecanoate to the mixture A obtained in step S1, stirring evenly to obtain a mixture B; S3, adding alkylphenol polyoxyethylene quaternary ammonium salt and chitosan quaternary ammonium salt to the mixture B obtained in step S2 in sequence, stirring evenly to obtain a mixture C; S4, slowly adding tripolyglycerol monostearate to the mixture C obtained in step S3, and stirring evenly to obtain a mixture D; S5, adding 2(3)-tert-butyl-4-hydroxyanisole and anti-phenol yellowing agent APY to the mixture D obtained in step S4 in sequence, stirring evenly to obtain a 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 process conditions are: high-speed stirring at a constant temperature of 55-65° C. for 30-35 min, and a stirring rate of 800-850 rpm; And / or, in step S2, the stirring process conditions are: stirring at a rate of 900-950 rpm for 20-25 min.

5. The preparation method according to claim 3, characterized in that: In step S3, the stirring process conditions are: stirring at a rate of 1200-1250 rpm for 30-35 min; after the mixture C system becomes viscous, the stirring rate is reduced to 850-900 rpm.

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

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

8. A polyamide fiber, characterized in that: The invention is made of the polyamide spinning oil according to claim 1 or 2 and the polyamide spinning oil prepared by the preparation method according to any one of claims 3 to 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 a breaking elongation of 20 to 50%.

10. A method for preparing polyamide fiber according to claim 8, characterized in that: The method comprises adding a polyamide spinning oil into a sizing tank of an oiling machine, then immersing unsized synthetic fibers into the polyamide spinning oil, and passing the fibers through the sizing tank of the oiling machine at a pulling speed of 5 to 2000 m / min, and winding the fibers after high-multiple stretching after exiting the tank to obtain the polyamide fibers.

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