Bi-component superfine spun-bonded spunlace non-woven material and preparation method thereof

Abstract

The invention discloses a bi-component superfine spun-bonded spunlace non-woven material and a preparation method thereof, and relates to the technical field of non-woven materials. The preparation method of the non-woven material comprises the following steps: S1, uniformly mixing a polyester master batch and a modified polyester master batch, and drying to obtain a PET master batch; s2, uniformly mixing and drying a chinlon 6 master batch and the modified chinlon 6 master batch to obtain a PA-6 master batch; S3, sequentially adding the PET master batch and the PA-6 master batch into a feed port of a corresponding double-screw extruder, and performing melt extrusion, side blowing traction spinning, lapping, spunlace splitting reinforcement and drying to obtain the bi-component superfine spunbond spunlace non-woven material. The non-woven material composed of the two-component superfine fibers is prepared through a spunbond method and a spunlace method, the non-woven material has good mechanical performance and small diameter fineness, the balance of the fiber splitting capacity and the mechanical performance is achieved, and meanwhile the hydrophilicity of the non-woven material is improved.

Description

Technical Field

[0001] This invention relates to the field of nonwoven materials technology, specifically a two-component ultrafine spunbond hydroentangled nonwoven material and its preparation method. Background Technology

[0002] Nonwoven fabrics refer to sheet or roll materials obtained by directly forming a web from fibers without traditional spinning and weaving processes, followed by heating and reinforcement. Based on the web-forming process, they are classified into several categories: spunbond, meltblown, hydroentangling, needle punching, and thermal bonding. Spunbond technology involves stretching molten polymer into ultrafine fibers using high-speed hot air, then directly cooling to form a web. It features extremely fine fibers and small pores, and is generally used for intermediate filtration and sound-absorbing functional layers. Hydroentangling technology uses high-pressure micro-water needles to entangle the fibers, resulting in a smooth and soft material, used in synthetic leather base fabrics.

[0003] The bicomponent spunbond hydroentangling process combines composite spinning technology with spunbond nonwoven technology. By using hydroentangling, composite filament fibers are peeled off and intertwined. The resulting material combines the technological and performance advantages of both spunbond and hydroentangled nonwoven materials. However, the existing bicomponent spunbond hydroentangling process still has some problems. For example, bicomponent materials are generally hydrophobic, and the prepared products have poor hydrophilicity and moisture permeability, requiring hydrophilic modification treatment after the finished product, which may lead to a decrease in the mechanical properties of the material. In the spunbond process, the smaller the fiber diameter, the easier it is to break during spinning, making it difficult to balance fineness and mechanical properties.

[0004] In summary, solving the above problems and preparing a two-component ultrafine spunbond hydroentangled nonwoven material is of great significance. Summary of the Invention

[0005] The purpose of this invention is to provide a two-component ultrafine spunbond hydroentangled nonwoven material and its preparation method, so as to solve the problems mentioned in the background art.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution: A method for preparing a two-component ultrafine spunbond hydroentangled nonwoven material includes the following steps: S1: Mix polyester masterbatch and modified polyester masterbatch evenly, and dry to obtain PET masterbatch; S2: Mix nylon 6 masterbatch and modified nylon 6 masterbatch evenly, and dry to obtain PA-6 masterbatch: S3: PET masterbatch and PA-6 masterbatch are added sequentially to the feed inlet of the corresponding twin-screw extruder, melt extruded, spun by side blowing, web laid, hydroentangled fiber opening and reinforcement, and dried to obtain a two-component ultrafine spunbond hydroentangled nonwoven material. The ratio of PET masterbatch to PA6 masterbatch is 50~60:40~50.

[0007] Preferably, the mass ratio of the polyester masterbatch to the modified polyester masterbatch is 20:6~7; the mass ratio of the nylon 6 masterbatch to the modified nylon 6 masterbatch is 20:6~7.

[0008] Preferredly, the preparation method of the modified polyester masterbatch includes the following steps: under a nitrogen atmosphere, dimethyl terephthalate, dimethyl 2,5-furandicarboxylate, ethylene glycol, modified montmorillonite, zinc acetate, and antimony glycol are mixed evenly, stirred at 180~200℃ for 2~3h, the temperature is increased to 260~270℃ and the pressure is reduced to 700~800Pa, stirred for 1~1.5h, the pressure is further reduced to 100~200Pa, and stirred for another 3~4h to obtain the modified polyester masterbatch.

[0009] Preferably, the modified polyester comprises the following raw materials in parts by weight: 29-31 parts dimethyl terephthalate, 3-3.1 parts dimethyl 2,5-furandicarboxylate, 15-16 parts ethylene glycol, 10-12 parts modified montmorillonite, 0.03-0.04 parts zinc acetate, and 0.14-0.15 parts antimony glycolate.

[0010] Preferred method for preparing modified montmorillonite includes the following steps: (1) Styrene, maleic anhydride, N-methyldiallylamine and azobisisobutyronitrile are added to isoamyl acetate under a nitrogen atmosphere and stirred evenly. The mixture is stirred and reacted at 70-80°C for 6-8 hours. The product is centrifuged, washed and dried to obtain maleic anhydride copolymer. (2) Add the maleic anhydride copolymer to a 35-40 wt% sodium hydroxide solution, stir at 30-40℃ for 40-60 min, adjust the pH to 5-6, remove the solvent by rotary evaporation, wash, and dry to obtain the hydrolyzed maleic anhydride copolymer. (3) Add hydrolyzed maleic anhydride copolymer and dibromoneopentyl glycol to ethanol and stir evenly. Stir at 65~70℃ for 48~72h, remove solvent by rotary evaporation, purify, and dry to obtain quaternized hydrolyzed maleic anhydride copolymer. (4) Add montmorillonite to deionized water and ultrasonically disperse it evenly. Add quaternized hydrolyzed maleic anhydride copolymer, stir at 60~65℃ for 2~3h, heat to 70~75℃ and age for 12~15h, centrifuge, wash and dry to obtain modified montmorillonite.

[0011] Preferably, the maleic anhydride copolymer comprises the following raw materials, in parts by mass: 5.1-5.3 parts styrene, 4.8-5.0 parts maleic anhydride, 2.7-2.9 parts N-methyldiallylamine, 0.07-0.08 parts azobisisobutyronitrile, and 70-80 parts isoamyl acetate; The quaternized hydrolyzed maleic anhydride copolymer comprises the following raw materials, in parts by mass: 12-14 parts hydrolyzed maleic anhydride copolymer, 6.5-6.6 parts dibromoneopentyl glycol, and 70-80 parts ethanol; The maleic anhydride copolymer comprises the following raw materials, by mass parts: 4.5-5.5 parts montmorillonite, 80-100 parts deionized water, and 9-10 parts quaternized hydrolyzed maleic anhydride copolymer.

[0012] Preferredly, the preparation method of the modified nylon 6 masterbatch includes the following steps: under a nitrogen atmosphere, caprolactam, 2,5-furandicarboxylic acid, ethylenediamine and modified montmorillonite are mixed evenly and stirred at 230~240℃ for 10~12h to obtain the modified nylon 6 masterbatch.

[0013] Preferably, the modified nylon 6 masterbatch comprises the following raw materials, by mass parts: 44-46 parts caprolactam, 3-3.4 parts 2,5-furandicarboxylic acid, 1.2-1.3 parts ethylenediamine, and 6-8 parts modified montmorillonite.

[0014] Preferably, during the hydroentangling fiber opening and reinforcement process, the hydroentangling energy is 18~24 J / g; during the side-blowing traction spinning process, the diameter of the bicomponent fibers is 10~15 μm, and the shape is hollow orange-petal type; the areal density of the bicomponent ultrafine spunbond hydroentangled nonwoven material is 100~120 g / m². 2 .

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: The present invention prepares modified polyester masterbatch and modified nylon 6 masterbatch respectively by using montmorillonite organic modification as a reinforcing filler, and uses it as the modifier corresponding to the two-component masterbatch. Nonwoven materials composed of two-component ultrafine fibers are prepared by spunbonding and hydroentangling methods. It has good mechanical properties and small diameter fineness, achieves a balance between fiber splitting ability and mechanical properties, and improves the hydrophilicity of nonwoven materials.

[0016] The method for organic modification of montmorillonite is as follows: styrene, maleic anhydride, and N-methyldiallylamine are copolymerized under the initiation of azobisisobutyronitrile to obtain a maleic anhydride copolymer. Then, the copolymer is added to a sodium hydroxide solution to hydrolyze the maleic anhydride groups and acidify them, resulting in a partially carboxyl-containing hydrolyzed maleic anhydride copolymer. Further, dibromoneopentyl glycol is used to modify the N-methyldiallylamine groups in the copolymer with quaternary ammonium. Finally, the copolymer chains are introduced into the interlayer of montmorillonite using an intercalation method to obtain modified montmorillonite.

[0017] Montmorillonite, with its nanosheet structure, can interact with polymer chain ends to form a network structure. Its introduction helps improve the mechanical properties of the fiber matrix and acts as a heat stabilizer, adsorbing small molecules and water from the polymer to reduce thermal degradation. Simultaneously, it acts as a nucleating agent, increasing the crystallization rate and production efficiency. Modifying montmorillonite using a styrene-maleic anhydride copolymer as a base helps improve its dispersibility in the matrix, enhancing fiber uniformity and mechanical properties. During traction spinning, it reduces the risk of accidental breakage, allowing for smaller fiber diameters. Furthermore, the maleic anhydride groups, through alkaline hydrolysis, generate carboxylates, further increasing the matrix's hydrophilicity. Adjusting the pH retains some carboxyl groups, facilitating subsequent grafting modification. Finally, using dibromoneopentyl glycol to modify the N-methyldiallylamine groups in the copolymer with quaternary ammonium compounds for intercalation modification introduces them into the montmorillonite interlayer, while the two hydroxyl groups further enhance the matrix's hydrophilicity.

[0018] The modified polyester masterbatch is prepared by transesterification and polycondensation of dimethyl terephthalate, dimethyl 2,5-furandicarboxylate, ethylene glycol, and modified montmorillonite under the catalysis of zinc acetate and antimony glycolate. The modified nylon 6 masterbatch is prepared by solid-phase polycondensation of caprolactam, 2,5-furandicarboxylic acid, 1.2-1.3 parts ethylenediamine, and 6-8 parts modified montmorillonite.

[0019] In this process, the copolymerization of montmorillonite with a structure similar to that of the masterbatch before use further promotes the dispersion of montmorillonite in the matrix, enhances mechanical properties, and ensures the presence of a large number of hydrophilic groups after grafting, thus maintaining the hydrophilicity of the matrix. Simultaneously, furan groups are introduced during the corresponding copolymerization modification process, which helps improve fiber mechanical properties while creating a certain similarity between the two components. Furthermore, the modified montmorillonite has a similar structure, which helps improve the compatibility and adhesion of the two components, preventing fiber splitting during spinning and improving fiber uniformity and mechanical properties. However, the amount of masterbatch prepared from modified montmorillonite needs to be limited; excessive content can lead to greater adhesion between the two components, reduced hydroentangling efficiency, and decreased water absorption of the material. Detailed Implementation

[0020] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] It should be noted that the following quantities are by weight. There are no special restrictions on the suppliers of any of the raw materials involved in this invention. Exemplary examples include: montmorillonite, specifically calcium-based montmorillonite, originating from Chifeng City, Inner Mongolia Autonomous Region, with a cation exchange capacity of 110 mmol / 100g and a particle size of 200 mesh; polyester masterbatch: PET, viscosity [ƞ] = 0.65 dL·g. -1 Nylon 6 masterbatch, PA-6, [ƞ] = 2.4 dL·g -1 CAS No. for styrene: 100-42-5; CAS No. for maleic anhydride: 108-31-6; CAS No. for N-methyldiallylamine: 2424-01-3; CAS No. for azobisisobutyronitrile: 78-67-1; CAS No. for isoamyl acetate: 123-92-2; CAS No. for dibromoneopentyl glycol: 3296-90-0; CAS No. for dimethyl terephthalate: 120-61-6 CAS No. 4282-32-0 for dimethyl 2,5-furandicarboxylate; CAS No. 107-21-1 for ethylene glycol; CAS No. 557-34-6 for zinc acetate; CAS No. 29736-75-2 for antimony glycol; CAS No. 105-60-2 for caprolactam; CAS No. 3238-40-2 for 2,5-furandicarboxylic acid; CAS No. 107-15-3 for ethylenediamine.

[0022] In the following examples, parts refer to parts by weight, and all raw materials used above and otherwise not mentioned are commercially available; wherein, the surface density of the nonwoven materials prepared in each example and comparative example is 120 g / m³. 2 .

[0023] Example 1: The preparation method of a two-component ultrafine spunbond hydroentangled nonwoven material includes the following steps: Step 1: Preparation of modified montmorillonite: (1) Under a nitrogen atmosphere, 5.2 parts of styrene, 4.9 parts of maleic anhydride, 2.8 parts of N-methyldiallylamine, and 0.07 parts of azobisisobutyronitrile were added to 80 parts of isoamyl acetate and stirred evenly. The mixture was stirred at 75°C for 6 hours. The product was centrifuged, washed, and dried to obtain the maleic anhydride copolymer. (2) The maleic anhydride copolymer was added to a 40wt% sodium hydroxide solution and stirred at 30°C for 60 minutes. The pH was adjusted to 5.5±0.1. The solvent was removed by rotary evaporation and the product was washed. , dried, to obtain hydrolyzed maleic anhydride copolymer; (3) 13 parts of hydrolyzed maleic anhydride copolymer and 6.5 parts of dibromoneopentyl glycol were added to 80 parts of ethanol and stirred evenly. The mixture was stirred at 65°C for 72 hours, the solvent was removed by rotary evaporation, purified, and dried to obtain quaternized hydrolyzed maleic anhydride copolymer; (4) 5 parts of montmorillonite were added to 100 parts of deionized water and ultrasonically dispersed evenly. 9.5 parts of quaternized hydrolyzed maleic anhydride copolymer were added and stirred at 60°C for 2 hours. The mixture was heated to 70°C and aged for 12 hours. The mixture was centrifuged, washed, and dried to obtain modified montmorillonite; Step 2: Preparation of modified polyester masterbatch: Under a nitrogen atmosphere, 30 parts of dimethyl terephthalate, 3.05 parts of dimethyl 2,5-furandicarboxylate, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, and 0.14 parts of antimony glycol were mixed evenly and stirred at 180°C for 2.5 hours. The temperature was then increased to 260°C and the pressure was reduced to 800 Pa. The mixture was stirred for 1.5 hours, and the pressure was further reduced to 200 Pa. The mixture was stirred for another 3 hours to obtain the modified polyester masterbatch. Step 3: Preparation of modified nylon 6 masterbatch: Under a nitrogen atmosphere, 45 parts of caprolactam, 3.5 parts of 2,5-furandicarboxylic acid, 1.2 parts of ethylenediamine and 7 parts of modified montmorillonite were mixed evenly and stirred at 240℃ for 12 hours to obtain modified nylon 6 masterbatch. Step 4: Preparation of bicomponent ultrafine spunbond hydroentangled nonwoven material: S1: Mix polyester masterbatch and modified polyester masterbatch evenly at a mass ratio of 20:7, and dry to obtain PET masterbatch; S2: Mix nylon 6 masterbatch and modified nylon 6 masterbatch at a mass ratio of 20:7 until homogeneous, then dry to obtain PA-6 masterbatch. S3: PET masterbatch and PA-6 masterbatch are added sequentially to the feed inlets of the corresponding twin-screw extruders at a ratio of 50:50. The heating temperatures of each zone of the PET masterbatch are 275℃, 280℃, 285℃, 285℃, 290℃, and 290℃, respectively. The heating temperatures of each zone of the PA-6 masterbatch are 250℃, 255℃, 255℃, 260℃, 260℃, and 260℃, respectively. The mixture is melt-extruded and cooled by side-blowing air at a temperature of 25℃ and a wind speed of 1m / s. The mixture is then spun into bicomponent fibers with a diameter of 12μm. The fibers are directly laid into a web and reinforced by hydroentangling with an energy of 24J / g. After drying, a bicomponent ultrafine spunbond hydroentangled nonwoven material is obtained.

[0024] Example 2: The preparation method of a two-component ultrafine spunbond hydroentangled nonwoven material includes the following steps: Step 1: Preparation of modified montmorillonite: (1) Under a nitrogen atmosphere, 5.2 parts of styrene, 4.9 parts of maleic anhydride, 2.8 parts of N-methyldiallylamine, and 0.07 parts of azobisisobutyronitrile were added to 80 parts of isoamyl acetate and stirred evenly. The mixture was stirred at 75°C for 6 hours. The product was centrifuged, washed, and dried to obtain the maleic anhydride copolymer. (2) The maleic anhydride copolymer was added to a 40wt% sodium hydroxide solution and stirred at 30°C for 60 minutes. The pH was adjusted to 5.5±0.1. The solvent was removed by rotary evaporation and the product was washed. , dried, to obtain hydrolyzed maleic anhydride copolymer; (3) 13 parts of hydrolyzed maleic anhydride copolymer and 6.5 parts of dibromoneopentyl glycol were added to 80 parts of ethanol and stirred evenly. The mixture was stirred at 65°C for 72 hours, the solvent was removed by rotary evaporation, purified, and dried to obtain quaternized hydrolyzed maleic anhydride copolymer; (4) 5 parts of montmorillonite were added to 100 parts of deionized water and ultrasonically dispersed evenly. 9.5 parts of quaternized hydrolyzed maleic anhydride copolymer were added and stirred at 60°C for 2 hours. The mixture was heated to 70°C and aged for 12 hours. The mixture was centrifuged, washed, and dried to obtain modified montmorillonite; Step 2: Preparation of modified polyester masterbatch: Under a nitrogen atmosphere, 30 parts of dimethyl terephthalate, 3.05 parts of dimethyl 2,5-furandicarboxylate, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, and 0.14 parts of antimony glycol were mixed evenly and stirred at 180°C for 2.5 hours. The temperature was then increased to 260°C and the pressure was reduced to 800 Pa. The mixture was stirred for 1.5 hours, and the pressure was further reduced to 200 Pa. The mixture was stirred for another 3 hours to obtain the modified polyester masterbatch. Step 3: Preparation of modified nylon 6 masterbatch: Under a nitrogen atmosphere, 45 parts of caprolactam, 3.5 parts of 2,5-furandicarboxylic acid, 1.2 parts of ethylenediamine and 7 parts of modified montmorillonite were mixed evenly and stirred at 240℃ for 12 hours to obtain modified nylon 6 masterbatch. Step 4: Preparation of bicomponent ultrafine spunbond hydroentangled nonwoven material: S1: Mix polyester masterbatch and modified polyester masterbatch at a mass ratio of 20:6, dry them, and obtain PET masterbatch; S2: Mix nylon 6 masterbatch and modified nylon 6 masterbatch at a mass ratio of 20:6 until homogeneous, then dry to obtain PA-6 masterbatch. S3: PET masterbatch and PA-6 masterbatch are added sequentially to the feed inlets of the corresponding twin-screw extruders at a ratio of 50:50. The heating temperatures of each zone of the PET masterbatch are 275℃, 280℃, 285℃, 285℃, 290℃, and 290℃, respectively. The heating temperatures of each zone of the PA-6 masterbatch are 250℃, 255℃, 255℃, 260℃, 260℃, and 260℃, respectively. The mixture is melt-extruded and cooled by side-blowing air at a temperature of 25℃ and a wind speed of 1m / s. The mixture is then spun into bicomponent fibers with a diameter of 12μm. The fibers are directly laid into a web and reinforced by hydroentangling with an energy of 24J / g. After drying, a bicomponent ultrafine spunbond hydroentangled nonwoven material is obtained.

[0025] Example 3: The preparation method of a two-component ultrafine spunbond hydroentangled nonwoven material includes the following steps: Step 1: Preparation of modified montmorillonite: (1) Under a nitrogen atmosphere, 5.2 parts of styrene, 4.9 parts of maleic anhydride, 2.8 parts of N-methyldiallylamine, and 0.07 parts of azobisisobutyronitrile were added to 80 parts of isoamyl acetate and stirred evenly. The mixture was stirred at 75°C for 6 hours. The product was centrifuged, washed, and dried to obtain the maleic anhydride copolymer. (2) The maleic anhydride copolymer was added to a 40wt% sodium hydroxide solution and stirred at 30°C for 60 minutes. The pH was adjusted to 5.5±0.1. The solvent was removed by rotary evaporation and the product was washed. , dried, to obtain hydrolyzed maleic anhydride copolymer; (3) 13 parts of hydrolyzed maleic anhydride copolymer and 6.5 parts of dibromoneopentyl glycol were added to 80 parts of ethanol and stirred evenly. The mixture was stirred at 65°C for 72 hours, the solvent was removed by rotary evaporation, purified, and dried to obtain quaternized hydrolyzed maleic anhydride copolymer; (4) 5 parts of montmorillonite were added to 100 parts of deionized water and ultrasonically dispersed evenly. 9.5 parts of quaternized hydrolyzed maleic anhydride copolymer were added and stirred at 60°C for 2 hours. The mixture was heated to 70°C and aged for 12 hours. The mixture was centrifuged, washed, and dried to obtain modified montmorillonite; Step 2: Preparation of modified polyester masterbatch: Under a nitrogen atmosphere, 30 parts of dimethyl terephthalate, 3.05 parts of dimethyl 2,5-furandicarboxylate, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, and 0.14 parts of antimony glycol were mixed evenly and stirred at 180°C for 2.5 hours. The temperature was then increased to 260°C and the pressure was reduced to 800 Pa. The mixture was stirred for 1.5 hours, and the pressure was further reduced to 200 Pa. The mixture was stirred for another 3 hours to obtain the modified polyester masterbatch. Step 3: Preparation of modified nylon 6 masterbatch: Under a nitrogen atmosphere, 45 parts of caprolactam, 3.5 parts of 2,5-furandicarboxylic acid, 1.2 parts of ethylenediamine and 7 parts of modified montmorillonite were mixed evenly and stirred at 240℃ for 12 hours to obtain modified nylon 6 masterbatch. Step 4: Preparation of bicomponent ultrafine spunbond hydroentangled nonwoven material: S1: Mix polyester masterbatch and modified polyester masterbatch evenly at a mass ratio of 20:7, and dry to obtain PET masterbatch; S2: Mix nylon 6 masterbatch and modified nylon 6 masterbatch at a mass ratio of 20:7 until homogeneous, then dry to obtain PA-6 masterbatch. S3: PET masterbatch and PA-6 masterbatch are added sequentially to the feed inlets of the corresponding twin-screw extruders at a ratio of 60:40. The heating temperatures of each zone of the PET masterbatch are 275℃, 280℃, 285℃, 285℃, 290℃, and 290℃, respectively. The heating temperatures of each zone of the PA-6 masterbatch are 250℃, 255℃, 255℃, 260℃, 260℃, and 260℃, respectively. The mixture is melt-extruded and cooled by side-blowing air at a temperature of 25℃ and a wind speed of 1m / s. The mixture is then spun into bicomponent fibers with a diameter of 12μm. The fibers are directly laid into a web and reinforced by hydroentangling with an energy of 24J / g. After drying, a bicomponent ultrafine spunbond hydroentangled nonwoven material is obtained.

[0026] Comparative Example 1: Based on Example 1, montmorillonite was modified using only hexadecyltrimethylammonium bromide, with the remaining processes unchanged, as shown in the following steps: Step 1: Preparation of modified montmorillonite: Add 5 parts of montmorillonite to 100 parts of deionized water and ultrasonically disperse evenly. Add 3 parts of hexadecyltrimethylammonium bromide, stir at 60℃ for 2 hours, heat to 70℃ and age for 12 hours. Centrifuge, wash, and dry to obtain modified montmorillonite. Step 2: Preparation of modified polyester masterbatch: Under a nitrogen atmosphere, 30 parts of dimethyl terephthalate, 3.05 parts of dimethyl 2,5-furandicarboxylate, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, and 0.14 parts of antimony glycol were mixed evenly and stirred at 180°C for 2.5 hours. The temperature was then increased to 260°C and the pressure was reduced to 800 Pa. The mixture was stirred for 1.5 hours, and the pressure was further reduced to 200 Pa. The mixture was stirred for another 3 hours to obtain the modified polyester masterbatch. Step 3: Preparation of modified nylon 6 masterbatch: Under a nitrogen atmosphere, 45 parts of caprolactam, 3.5 parts of 2,5-furandicarboxylic acid, 1.2 parts of ethylenediamine and 7 parts of modified montmorillonite were mixed evenly and stirred at 240℃ for 12 hours to obtain modified nylon 6 masterbatch. Step 4: Preparation of bicomponent ultrafine spunbond hydroentangled nonwoven material: S1: Mix polyester masterbatch and modified polyester masterbatch evenly at a mass ratio of 20:7, and dry to obtain PET masterbatch; S2: Mix nylon 6 masterbatch and modified nylon 6 masterbatch at a mass ratio of 20:7 until homogeneous, then dry to obtain PA-6 masterbatch. S3: PET masterbatch and PA-6 masterbatch are added sequentially to the feed inlets of the corresponding twin-screw extruders at a ratio of 50:50. The heating temperatures of each zone of the PET masterbatch are 275℃, 280℃, 285℃, 285℃, 290℃, and 290℃, respectively. The heating temperatures of each zone of the PA-6 masterbatch are 250℃, 255℃, 255℃, 260℃, 260℃, and 260℃, respectively. The mixture is melt-extruded and cooled by side-blowing air at a temperature of 25℃ and a wind speed of 1m / s. The mixture is then spun into bicomponent fibers with a diameter of 12μm. The fibers are directly laid into a web and reinforced by hydroentangling with an energy of 24J / g. After drying, a bicomponent ultrafine spunbond hydroentangled nonwoven material is obtained.

[0027] Comparative Example 2: Based on Example 1, the amount of modified polyester masterbatch and modified nylon 6 masterbatch was increased, while the rest of the process remained unchanged. The specific steps are as follows: Step 1: Preparation of modified montmorillonite: (1) Under a nitrogen atmosphere, 5.2 parts of styrene, 4.9 parts of maleic anhydride, 2.8 parts of N-methyldiallylamine, and 0.07 parts of azobisisobutyronitrile were added to 80 parts of isoamyl acetate and stirred evenly. The mixture was stirred at 75°C for 6 hours. The product was centrifuged, washed, and dried to obtain the maleic anhydride copolymer. (2) The maleic anhydride copolymer was added to a 40wt% sodium hydroxide solution and stirred at 30°C for 60 minutes. The pH was adjusted to 5.5±0.1. The solvent was removed by rotary evaporation and the product was washed. , dried, to obtain hydrolyzed maleic anhydride copolymer; (3) 13 parts of hydrolyzed maleic anhydride copolymer and 6.5 parts of dibromoneopentyl glycol were added to 80 parts of ethanol and stirred evenly. The mixture was stirred at 65°C for 72 hours, the solvent was removed by rotary evaporation, purified, and dried to obtain quaternized hydrolyzed maleic anhydride copolymer; (4) 5 parts of montmorillonite were added to 100 parts of deionized water and ultrasonically dispersed evenly. 9.5 parts of quaternized hydrolyzed maleic anhydride copolymer were added and stirred at 60°C for 2 hours. The mixture was heated to 70°C and aged for 12 hours. The mixture was centrifuged, washed, and dried to obtain modified montmorillonite; Step 2: Preparation of modified polyester masterbatch: Under a nitrogen atmosphere, 30 parts of dimethyl terephthalate, 3.05 parts of dimethyl 2,5-furandicarboxylate, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, and 0.14 parts of antimony glycol were mixed evenly and stirred at 180°C for 2.5 hours. The temperature was then increased to 260°C and the pressure was reduced to 800 Pa. The mixture was stirred for 1.5 hours, and the pressure was further reduced to 200 Pa. The mixture was stirred for another 3 hours to obtain the modified polyester masterbatch. Step 3: Preparation of modified nylon 6 masterbatch: Under a nitrogen atmosphere, 45 parts of caprolactam, 3.5 parts of 2,5-furandicarboxylic acid, 1.2 parts of ethylenediamine and 7 parts of modified montmorillonite were mixed evenly and stirred at 240℃ for 12 hours to obtain modified nylon 6 masterbatch. Step 4: Preparation of bicomponent ultrafine spunbond hydroentangled nonwoven material: S1: Mix polyester masterbatch and modified polyester masterbatch at a mass ratio of 20:12, dry them, and obtain PET masterbatch; S2: Mix nylon 6 masterbatch and modified nylon 6 masterbatch at a mass ratio of 20:12 until homogeneous, then dry to obtain PA-6 masterbatch. S3: PET masterbatch and PA-6 masterbatch are added sequentially to the feed inlets of the corresponding twin-screw extruders at a ratio of 50:50. The heating temperatures of each zone of the PET masterbatch are 275℃, 280℃, 285℃, 285℃, 290℃, and 290℃, respectively. The heating temperatures of each zone of the PA-6 masterbatch are 250℃, 255℃, 255℃, 260℃, 260℃, and 260℃, respectively. The mixture is melt-extruded and cooled by side-blowing air at a temperature of 25℃ and a wind speed of 1m / s. The mixture is then spun into bicomponent fibers with a diameter of 12μm. The fibers are directly laid into a web and reinforced by hydroentangling with an energy of 24J / g. After drying, a bicomponent ultrafine spunbond hydroentangled nonwoven material is obtained.

[0028] Comparative Example 3: Based on Example 1, dimethyl 2,5-furandicarboxylate was not added during the preparation of the modified polyester masterbatch, and the rest of the process remained unchanged, as shown in the following steps: Step 1: Preparation of modified montmorillonite: (1) Under a nitrogen atmosphere, 5.2 parts of styrene, 4.9 parts of maleic anhydride, 2.8 parts of N-methyldiallylamine, and 0.07 parts of azobisisobutyronitrile were added to 80 parts of isoamyl acetate and stirred evenly. The mixture was stirred at 75°C for 6 hours. The product was centrifuged, washed, and dried to obtain the maleic anhydride copolymer. (2) The maleic anhydride copolymer was added to a 40wt% sodium hydroxide solution and stirred at 30°C for 60 minutes. The pH was adjusted to 5.5±0.1. The solvent was removed by rotary evaporation and the product was washed. , dried, to obtain hydrolyzed maleic anhydride copolymer; (3) 13 parts of hydrolyzed maleic anhydride copolymer and 6.5 parts of dibromoneopentyl glycol were added to 80 parts of ethanol and stirred evenly. The mixture was stirred at 65°C for 72 hours, the solvent was removed by rotary evaporation, purified, and dried to obtain quaternized hydrolyzed maleic anhydride copolymer; (4) 5 parts of montmorillonite were added to 100 parts of deionized water and ultrasonically dispersed evenly. 9.5 parts of quaternized hydrolyzed maleic anhydride copolymer were added and stirred at 60°C for 2 hours. The mixture was heated to 70°C and aged for 12 hours. The mixture was centrifuged, washed, and dried to obtain modified montmorillonite; Step 2: Preparation of modified polyester masterbatch: Under a nitrogen atmosphere, 33.05 parts of dimethyl terephthalate, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, and 0.14 parts of antimony glycol were mixed evenly and stirred at 180°C for 2.5 hours. The temperature was then increased to 260°C and the pressure was reduced to 800 Pa. The mixture was stirred for 1.5 hours, and the pressure was further reduced to 200 Pa. The mixture was stirred for another 3 hours to obtain the modified polyester masterbatch. Step 3: Preparation of modified nylon 6 masterbatch: Under a nitrogen atmosphere, 45 parts of caprolactam, 3.5 parts of 2,5-furandicarboxylic acid, 1.2 parts of ethylenediamine and 7 parts of modified montmorillonite were mixed evenly and stirred at 240℃ for 12 hours to obtain modified nylon 6 masterbatch. Step 4: Preparation of bicomponent ultrafine spunbond hydroentangled nonwoven material: S1: Mix polyester masterbatch and modified polyester masterbatch evenly at a mass ratio of 20:7, and dry to obtain PET masterbatch; S2: Mix nylon 6 masterbatch and modified nylon 6 masterbatch at a mass ratio of 20:7 until homogeneous, then dry to obtain PA-6 masterbatch. S3: PET masterbatch and PA-6 masterbatch are added sequentially to the feed inlets of the corresponding twin-screw extruders at a ratio of 50:50. The heating temperatures of each zone of the PET masterbatch are 275℃, 280℃, 285℃, 285℃, 290℃, and 290℃, respectively. The heating temperatures of each zone of the PA-6 masterbatch are 250℃, 255℃, 255℃, 260℃, 260℃, and 260℃, respectively. The mixture is melt-extruded and cooled by side-blowing air at a temperature of 25℃ and a wind speed of 1m / s. The mixture is then spun into bicomponent fibers with a diameter of 12μm. The fibers are directly laid into a web and reinforced by hydroentangling with an energy of 24J / g. After drying, a bicomponent ultrafine spunbond hydroentangled nonwoven material is obtained.

[0029] Comparative Example 4: Based on Example 1, 2,5-furandicarboxylic acid was not added during the preparation of the modified nylon masterbatch, and the remaining processes remained unchanged, as shown in the following steps: Step 1: Preparation of modified montmorillonite: (1) Under a nitrogen atmosphere, 5.2 parts of styrene, 4.9 parts of maleic anhydride, 2.8 parts of N-methyldiallylamine, and 0.07 parts of azobisisobutyronitrile were added to 80 parts of isoamyl acetate and stirred evenly. The mixture was stirred at 75°C for 6 hours. The product was centrifuged, washed, and dried to obtain the maleic anhydride copolymer. (2) The maleic anhydride copolymer was added to a 40wt% sodium hydroxide solution and stirred at 30°C for 60 minutes. The pH was adjusted to 5.5±0.1. The solvent was removed by rotary evaporation and the product was washed. , dried, to obtain hydrolyzed maleic anhydride copolymer; (3) 13 parts of hydrolyzed maleic anhydride copolymer and 6.5 parts of dibromoneopentyl glycol were added to 80 parts of ethanol and stirred evenly. The mixture was stirred at 65°C for 72 hours, the solvent was removed by rotary evaporation, purified, and dried to obtain quaternized hydrolyzed maleic anhydride copolymer; (4) 5 parts of montmorillonite were added to 100 parts of deionized water and ultrasonically dispersed evenly. 9.5 parts of quaternized hydrolyzed maleic anhydride copolymer were added and stirred at 60°C for 2 hours. The mixture was heated to 70°C and aged for 12 hours. The mixture was centrifuged, washed, and dried to obtain modified montmorillonite; Step 2: Preparation of modified polyester masterbatch: Under a nitrogen atmosphere, 30 parts of dimethyl terephthalate, 3.05 parts of dimethyl 2,5-furandicarboxylate, 15.5 parts of ethylene glycol, 11 parts of modified montmorillonite, 0.03 parts of zinc acetate, and 0.14 parts of antimony glycol were mixed evenly and stirred at 180°C for 2.5 hours. The temperature was then increased to 260°C and the pressure was reduced to 800 Pa. The mixture was stirred for 1.5 hours, and the pressure was further reduced to 200 Pa. The mixture was stirred for another 3 hours to obtain the modified polyester masterbatch. Step 3: Preparation of modified nylon 6 masterbatch: Under a nitrogen atmosphere, 45 parts of caprolactam, 3.3 parts of adipic acid, 1.2 parts of ethylenediamine and 7 parts of modified montmorillonite were mixed evenly and stirred at 240℃ for 12 hours to obtain modified nylon 6 masterbatch. Step 4: Preparation of bicomponent ultrafine spunbond hydroentangled nonwoven material: S1: Mix polyester masterbatch and modified polyester masterbatch evenly at a mass ratio of 20:7, and dry to obtain PET masterbatch; S2: Mix nylon 6 masterbatch and modified nylon 6 masterbatch at a mass ratio of 20:7 until homogeneous, then dry to obtain PA-6 masterbatch. S3: PET masterbatch and PA-6 masterbatch are added sequentially to the feed inlets of the corresponding twin-screw extruders at a ratio of 50:50. The heating temperatures of each zone of the PET masterbatch are 275℃, 280℃, 285℃, 285℃, 290℃, and 290℃, respectively. The heating temperatures of each zone of the PA-6 masterbatch are 250℃, 255℃, 255℃, 260℃, 260℃, and 260℃, respectively. The mixture is melt-extruded and cooled by side-blowing air at a temperature of 25℃ and a wind speed of 1m / s. The mixture is then spun into bicomponent fibers with a diameter of 12μm. The fibers are directly laid into a web and reinforced by hydroentangling with an energy of 24J / g. After drying, a bicomponent ultrafine spunbond hydroentangled nonwoven material is obtained.

[0030] Performance testing: (1) The tensile properties of the samples prepared in each embodiment and comparative example were tested using a universal testing machine according to GB / T 24218.3-2010; wherein the sample length was 30cm, the width was 5cm, and the tensile rate was 100m / min; (2) The tearing properties of the samples prepared in each embodiment and comparative example were tested using a universal testing machine according to GB / T 3917.2-2009; wherein the sample length was 30cm, the width was 5cm, and the tensile rate was 100m / min; (3) The water absorption properties of each embodiment and comparative example were tested according to GB / T 21655.1-2023; wherein the sample length was 10cm and the width was 10cm. The experimental data are shown in the table below.

[0031]

[0032] Conclusion: As shown in the table, this invention prepared modified polyester masterbatch and modified nylon 6 masterbatch by using montmorillonite organic modification as a reinforcing filler, and used it as the modifier corresponding to the two-component masterbatch. Nonwoven materials composed of two-component ultrafine fibers were prepared by spunbonding and hydroentangling. These materials have good mechanical properties and small diameter fineness, achieving a balance between fiber splitting ability and mechanical properties, and improving the hydrophilicity of the nonwoven materials.

[0033] In Comparative Example 1, montmorillonite was modified only with hexadecyltrimethylammonium bromide, resulting in weak dispersion and a lack of reinforcing segments and hydrophilic groups. Consequently, its mechanical properties decreased significantly, and its absorption time was longer. In Comparative Example 2, the addition of modified polyester masterbatch and modified nylon 6 masterbatch increased the adhesion between the two components, reduced the hydroentangling fiber opening efficiency, and consequently decreased the water absorption of the material. In Comparative Examples 3 and 4, furan groups were not introduced into the single modified masterbatch. This resulted in a certain decrease in the similarity between the two components, reduced compatibility and adhesion, fiber splitting during spinning, decreased fiber uniformity, and a slight decrease in mechanical properties.

[0034] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a two-component ultrafine spunbond hydroentangled nonwoven material, characterized in that, Includes the following steps: S1: Mix polyester masterbatch and modified polyester masterbatch evenly, and dry to obtain PET masterbatch; S2: Mix nylon 6 masterbatch and modified nylon 6 masterbatch evenly, and dry to obtain PA-6 masterbatch: S3: PET masterbatch and PA-6 masterbatch are added sequentially to the feed inlet of the corresponding twin-screw extruder, melt extruded, spun by side blowing, web laid, hydroentangled fiber opening and reinforcement, and dried to obtain a two-component ultrafine spunbond hydroentangled nonwoven material. The ratio of PET masterbatch to PA6 masterbatch is 50~60:40~50.

2. The method for preparing a bicomponent ultrafine spunbond hydroentangled nonwoven material according to claim 1, characterized in that: The mass ratio of the polyester masterbatch to the modified polyester masterbatch is 20:6~7; the mass ratio of the nylon 6 masterbatch to the modified nylon 6 masterbatch is 20:6~7.

3. The method for preparing a bicomponent ultrafine spunbond hydroentangled nonwoven material according to claim 1, characterized in that: The preparation method of the modified polyester masterbatch includes the following steps: under a nitrogen atmosphere, dimethyl terephthalate, dimethyl 2,5-furandicarboxylate, ethylene glycol, modified montmorillonite, zinc acetate, and antimony glycol are mixed evenly, stirred at 180~200℃ for 2~3h, the temperature is increased to 260~270℃ and the pressure is reduced to 700~800Pa, stirred for 1~1.5h, the pressure is further reduced to 100~200Pa, and stirred for another 3~4h to obtain the modified polyester masterbatch.

4. The method for preparing a bicomponent ultrafine spunbond hydroentangled nonwoven material according to claim 3, characterized in that: The modified polyester comprises the following raw materials, by mass parts: 29-31 parts dimethyl terephthalate, 3-3.1 parts dimethyl 2,5-furandicarboxylate, 15-16 parts ethylene glycol, 10-12 parts modified montmorillonite, 0.03-0.04 parts zinc acetate, and 0.14-0.15 parts antimony glycolate.

5. The method for preparing a bicomponent ultrafine spunbond hydroentangled nonwoven material according to claim 3, characterized in that: The preparation method of the modified montmorillonite includes the following steps: (1) Under a nitrogen atmosphere, styrene, maleic anhydride, N-methyldiallylamine and azobisisobutyronitrile are added to isoamyl acetate and stirred evenly. The mixture is stirred and reacted at 70~80℃ for 6~8h. The product is centrifuged, washed and dried to obtain maleic anhydride copolymer. (2) Add the maleic anhydride copolymer to a 35-40 wt% sodium hydroxide solution, stir at 30-40℃ for 40-60 min, adjust the pH to 5-6, remove the solvent by rotary evaporation, wash, and dry to obtain the hydrolyzed maleic anhydride copolymer. (3) Add hydrolyzed maleic anhydride copolymer and dibromoneopentyl glycol to ethanol and stir evenly. Stir at 65~70℃ for 48~72h, remove solvent by rotary evaporation, purify, and dry to obtain quaternized hydrolyzed maleic anhydride copolymer. (4) Add montmorillonite to deionized water and ultrasonically disperse it evenly. Add quaternized hydrolyzed maleic anhydride copolymer, stir at 60~65℃ for 2~3h, heat to 70~75℃ and age for 12~15h, centrifuge, wash and dry to obtain modified montmorillonite.

6. The method for preparing a bicomponent ultrafine spunbond hydroentangled nonwoven material according to claim 5, characterized in that: The maleic anhydride copolymer comprises the following raw materials, in parts by mass: 5.1-5.3 parts styrene, 4.8-5.0 parts maleic anhydride, 2.7-2.9 parts N-methyldiallylamine, 0.07-0.08 parts azobisisobutyronitrile, and 70-80 parts isoamyl acetate; The quaternized hydrolyzed maleic anhydride copolymer comprises the following raw materials, in parts by mass: 12-14 parts hydrolyzed maleic anhydride copolymer, 6.5-6.6 parts dibromoneopentyl glycol, and 70-80 parts ethanol; The maleic anhydride copolymer comprises the following raw materials, by mass parts: 4.5-5.5 parts montmorillonite, 80-100 parts deionized water, and 9-10 parts quaternized hydrolyzed maleic anhydride copolymer.

7. The method for preparing a bicomponent ultrafine spunbond hydroentangled nonwoven material according to claim 1, characterized in that: The preparation method of the modified nylon 6 masterbatch includes the following steps: under a nitrogen atmosphere, caprolactam, 2,5-furandicarboxylic acid, ethylenediamine and modified montmorillonite are mixed evenly and stirred at 230~240℃ for 10~12h to obtain modified nylon 6 masterbatch.

8. The method for preparing a bicomponent ultrafine spunbond hydroentangled nonwoven material according to claim 7, characterized in that: The modified nylon 6 masterbatch comprises the following raw materials, by mass parts: 44-46 parts caprolactam, 3-3.4 parts 2,5-furandicarboxylic acid, 1.2-1.3 parts ethylenediamine, and 6-8 parts modified montmorillonite.

9. The method for preparing a bicomponent ultrafine spunbond hydroentangled nonwoven material according to claim 1, characterized in that: During the hydroentanglement fiber opening and reinforcement process, the hydroentanglement energy is 18~24J / g; during the side-blowing traction spinning process, the diameter of the bicomponent fibers is 10~15μm, and the shape is hollow orange-petal-shaped; the areal density of the bicomponent ultrafine spunbond hydroentangled nonwoven material is 100~120g / m³. 2 .

10. The bicomponent ultrafine spunbond hydroentangled nonwoven material obtained by the preparation method of the bicomponent ultrafine spunbond hydroentangled nonwoven material according to any one of claims 1 to 9.

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