Abrasion-resistant waterproof composite type fleece fabric and preparation method thereof

Abstract

The application discloses a wear-resistant waterproof composite type fabric with a pile surface and a preparation method thereof, and relates to the technical field of textile fabric preparation.The technical scheme points of the application are as follows: nylon four-way stretch base cloth and a warm inner layer with single-brushing and single-rotating raising are selected, and a TPU waterproof and moisture-permeable film is arranged between the two; reaction type polyurethane hot melt adhesive is used to carry out point-shaped bonding in a relaxed state in which the warp and weft directions do not have elastic elongation after being subjected to an overfeed treatment, so as to construct an elastic buffer layer and a micropore channel; and finally, DWR durable water repellent treatment is carried out on the surface of the base cloth. By means of the overfeed composite process, internal stress is eliminated, and the non-continuous adhesive points are used as flexible hinges, so that the problems of easy edge curling, blistering and film layer fracture of the high-elastic fabric composite are effectively solved, and the fabric has the advantages of soft hand feeling, firm interlayer combination, size stability, excellent waterproof and moisture-permeable balance and washing resistance.

Description

Technical Field

[0001] This invention relates to the field of textile fabric preparation technology, and in particular to a wear-resistant and waterproof composite fleece fabric and its preparation method. Background Technology

[0002] With the increasing popularity of outdoor sports, the high-end outdoor equipment and functional apparel market is placing increasingly stringent demands on the overall performance of fabrics. Ideal outdoor functional fabrics need to simultaneously be waterproof, breathable, highly elastic, lightweight, warm, and skin-friendly.

[0003] Existing similar technologies mainly fall into two categories: The first category is single-layer waterproof and breathable fabrics, typically woven from high-density nylon or polyester fibers, combined with ePTFE or PU films and DWR coatings. While these fabrics can achieve high hydrostatic pressure resistance, they often suffer from a stiff feel and lack of elasticity. Furthermore, the single-layer structure lacks an inner lining, resulting in poor skin-friendliness when in direct contact with the skin, and insufficient static insulation performance.

[0004] The second type is double- or triple-layer composite thermal fabrics. The common structure is an outer windproof and waterproof membrane bonded to an inner fleece or other thermal insulation material through adhesive dots or lamination. Although this type of fabric has good warmth retention, in order to maintain the stability of the composite structure and the insulation effect, the finished product is often heavy and has high moisture resistance, which can easily cause a stuffy feeling during strenuous exercise.

[0005] To ensure the dimensional stability of the fabric and the integrity of the waterproof membrane under high hydrostatic pressure, existing technologies often sacrifice the fabric's two-way elasticity, limiting the freedom of movement of the human body during strenuous outdoor activities. Existing high-elasticity fabrics typically struggle to simultaneously achieve both lightweight design and a high level of waterproof performance.

[0006] Furthermore, in the pursuit of lightweight fabrics, the conventional approach is to use thinner base fabrics or reduce the insulation layer, which directly leads to a decrease in static warmth. Moreover, the inner coating can feel cold and sticky when in direct contact with the skin. If a thicker fleece layer is added to increase warmth and skin-friendliness, the fabric weight and thickness will increase dramatically, negating the advantages of lightweight design. Summary of the Invention

[0007] The purpose of this invention is to provide a method for preparing a wear-resistant and waterproof composite fleece fabric, which has the advantages of excellent waterproof and breathable properties, soft and elastic feel, stable structural dimensions, and high peel strength after washing.

[0008] The above-mentioned technical objective of the present invention is achieved through the following technical solution:

[0009] A method for preparing a wear-resistant and waterproof composite fleece-lined fabric includes the following steps:

[0010] Step S1: Prepare nylon four-sided elastic base fabric;

[0011] 86% nylon yarn and 14% spandex yarn are selected as raw materials, with the nylon yarn having a yarn count of 40D. The yarn is then interlaced to produce a nylon four-way elastic base fabric with both warp and weft elasticity.

[0012] Step S2: Prepare the thermal insulation inner layer;

[0013] Select a base fabric and perform a single-brush, single-shake napping process on it to form a nap layer on one side and a smooth bonding surface on the other side.

[0014] Step S3: Dot-like compounding;

[0015] A TPU waterproof and breathable film is selected and placed between the inner surface of the nylon four-way stretch base fabric and the bonding surface of the thermal insulation inner layer. Dot bonding is adopted, using a reactive polyurethane hot melt adhesive with discontinuous dot distribution. Under the condition of overfeed treatment and no elastic elongation in the warp and weft directions, the nylon four-way stretch base fabric, TPU waterproof and breathable film and thermal insulation inner layer are laminated into a whole structure. Dot bonding achieves lamination and composites while building an elastic buffer layer through discontinuous adhesive dots, and retains microporous channels for moisture penetration and elastic deformation space for the fabric to be stretched under stress in the un-adhesive areas.

[0016] Step S4: Surface functionalization treatment;

[0017] The outer surface of the composite nylon four-way elastic base fabric is treated with DWR durable water-repellent treatment.

[0018] Further details: In step S3, the TPU waterproof and breathable film is a hydrophilic modified non-porous polyurethane film, and the preparation process includes the following steps:

[0019] Step M1: Preparation of modified masterbatch;

[0020] Thermoplastic polyurethane resin chips are mixed with hydrophilic modifier, compatibilizer, antioxidant and opening agent in a certain proportion, and then reacted and granulated through a twin-screw extruder to obtain hydrophilic modified TPU masterbatch.

[0021] Step M2: Casting and film formation;

[0022] After being dehumidified and dried, the hydrophilic modified TPU masterbatch is added to the casting machine. The melt is conveyed under stable pressure and extruded through a T-die. It is then cast onto a cooling roller for cooling and shaping. After edge trimming, thickness measurement, and winding, a TPU waterproof and breathable film is obtained.

[0023] Further settings: Step M1 includes the following sub-steps:

[0024] Step M11: Mixing;

[0025] By weight, 100 parts of thermoplastic polyurethane resin chips, 15-25 parts of hydrophilic modifier, 3-5 parts of compatibilizer, 0.5-1.5 parts of antioxidant, and 1-3 parts of opening agent are added to a high-speed mixer and mixed at 30℃-40℃ for 10-20 minutes to obtain a premix.

[0026] Step M12, reaction extrusion;

[0027] The premixed material is added to a twin-screw extruder and reacted and blended at a temperature of 180℃-200℃ and a screw speed of 300r / min-500r / min. The mixture is then extruded into strands, granulated, and dried to obtain hydrophilic modified TPU masterbatch.

[0028] Further settings: The thermoplastic polyurethane resin chips are MDI-based polyester TPU; the hydrophilic modifier is polyethylene glycol or polyethylene oxide with a molecular weight of 4000-6000; the compatibilizer is TPU-PEG block copolymer or maleic anhydride-grafted TPU; the opening agent is porous silica micropowder with a particle size of 2μm-5μm.

[0029] Further settings: Step M2 includes the following sub-steps:

[0030] Step M21: Raw material drying; The hydrophilic modified TPU masterbatch is vacuum dried at 100℃-110℃ and dew point temperature below -40℃ for 3h-5h, so that the moisture content of the hydrophilic modified TPU masterbatch is less than 0.02%;

[0031] Step M22, stabilizing melt extrusion: The dried masterbatch is transported to a single screw extruder for melting. After the melt is stabilized by a melt gear pump, it enters the T-die. The temperature of the T-die is controlled at 205℃-215℃, so that the melt is extruded in a curtain shape.

[0032] Step M23: Casting and setting;

[0033] The surface temperature of the quenching roller is controlled at 15℃-25℃, so that the extruded melt can be rapidly cooled and crystallized on the quenching roller. By controlling the casting speed, the thickness of the formed TPU waterproof and breathable film is 0.015mm-0.020mm.

[0034] Further configuration: In step S1, the raw material of the nylon four-way stretch base fabric includes 86% nylon yarn and 14% spandex yarn by weight percentage, wherein the nylon yarn has a yarn count of 40D;

[0035] In step S2, the base fabric is a fleece base fabric with a weight of 180 g / m². 2 .

[0036] Further settings: Step S3 includes the following sub-steps:

[0037] Step S31: Hot melt adhesive dot transfer coating;

[0038] A reactive polyurethane hot melt adhesive with an elongation at break greater than 500% was selected as the adhesive. The reactive polyurethane hot melt adhesive was heated and melted. A gravure roller with a dot matrix pattern engraved on the surface was used for transfer coating. The molten hot melt adhesive was applied to the inner surface of the nylon four-way elastic base fabric in a discontinuous dot pattern. The amount of adhesive applied was controlled to be 10g / m² to 20g / m².

[0039] Step S32: Three-layer pressure lamination;

[0040] During the open time of the hot melt adhesive, the TPU waterproof and breathable film and the thermal insulation inner layer are introduced, and the overfeed rate of the nylon four-way elastic base fabric is controlled at 2%-5%, so that the nylon four-way elastic base fabric enters the composite area without elastic elongation. The three-layer materials are then laminated under pressure by a constant temperature pressure roller.

[0041] Step S33: Maturation and shaping;

[0042] The laminated fabric is rolled up and left to stand at 40°C to 50°C for 24 to 48 hours to allow the reactive polyurethane hot melt adhesive to complete cross-linking and curing.

[0043] Further settings: Step S4 includes the following sub-steps:

[0044] Step S41: Preparation of waterproofing working solution;

[0045] Using water as a medium, prepare a waterproof working solution containing 20g / L-60g / L of organic fluorine waterproofing agent or fluorine-free waterproofing agent and 5g / L-15g / L of blocked isocyanate crosslinking agent, and adjust the pH value of the working solution to 4.0-6.0.

[0046] Step S42: Immersion in liquid;

[0047] The composite fabric is immersed in the waterproof working liquid, and then the liquid is applied by a uniform rolling mill, with the residual rate controlled at 60%-80%, so that the waterproof working liquid is evenly attached to the surface of the fabric fibers.

[0048] Step S43: High-temperature baking and curing;

[0049] The impregnated fabric is fed into a setting machine and treated using a segmented temperature control method. First, it is pre-dried at 100℃-120℃ to remove moisture from the fabric surface. Then, it is baked and cured at 160℃-170℃ for 45-90 seconds to allow the waterproofing agent to form a cross-linked film structure on the fiber surface.

[0050] Further configuration: In step S1, the yarn structure of the nylon four-way stretch base fabric is as follows: both the warp and weft directions are made of semi-dull stretch textured yarn with specifications of 40D / 36F and 20D spandex yarn, which are interwoven together.

[0051] Another objective of this invention is to provide a wear-resistant and waterproof composite fleece fabric, which is prepared using the above-described method.

[0052] Further settings:

[0053] In summary, the present invention has the following beneficial effects:

[0054] First, in this invention, through steps S1 and S2, a nylon four-way stretch base fabric is prepared by interweaving 86% nylon yarn and 14% spandex yarn, and a warm inner layer with a smooth bonding surface is prepared using a single-brush, single-shake napping process. The high spandex content gives the base fabric excellent elastic recovery, while the smooth bonding surface provides a uniform wetting and spreading interface for the adhesive. This effectively reduces the micro-roughness difference at the composite interface, preventing excessive adhesive penetration or weak adhesion caused by uneven surfaces. This solves the problem of stiff hand feel or insufficient peel strength that often occurs when high-elasticity fabrics are laminated with long-pile fabrics, resulting in a soft overall feel and strong interlayer bonding.

[0055] In step S3, a dot-matrix bonding process is employed, utilizing a reactive polyurethane hot melt adhesive with a discontinuous dot-matrix distribution. This adhesive is laminated under overfeed conditions and in a state where elastic elongation has not occurred in the warp and weft directions. During curing, the reactive polyurethane hot melt adhesive undergoes a chemical cross-linking reaction, forming a network macromolecular structure. The synergistic effect of the overfeed treatment and the absence of elastic elongation ensures that the adhesive's cross-linking and curing process is conducted in a low-stress environment. This prevents shear stress caused by the pre-stretching and shrinkage of the base fabric from damaging the adhesive interface or causing wrinkling of the TPU waterproof and breathable film. This combination of a chemically cross-linked network and a physically relaxed state effectively solves the problems of edge curling, bubbling, and film breakage caused by stress release during the production and use of elastic composite fabrics, improving the dimensional stability and washability of the finished product.

[0056] Furthermore, an elastic buffer layer is constructed using discontinuous adhesive dots, while retaining microporous channels for moisture penetration and elastic deformation space for fabric under tension in unadhesive areas. Utilizing the elastic modulus properties of the cured reactive polyurethane hot melt adhesive, it acts as a flexible hinge connecting the nylon four-way stretch base fabric and the TPU waterproof and breathable film. When the fabric is stretched by external force, the elastic buffer layer absorbs and disperses the deformation stress transmitted by the nylon four-way stretch base fabric, providing cushioning protection for the TPU waterproof and breathable film and preventing damage to the film's microstructure due to rigid stretching. Simultaneously, the retained microporous channels ensure a free path for moisture molecules to penetrate, significantly reducing moisture resistance while maintaining high hydrostatic pressure resistance. This resolves the technical contradiction of sacrificing breathability for waterproofing in traditional full-coating or tight-fitting processes, resulting in an excellent balance between waterproofing and breathability, and superior wearing comfort.

[0057] By applying a DWR (Durable Water Repellent) treatment to the outer surface of the composite nylon four-way stretch base fabric, the surface energy of the fiber surface is reduced using organic or fluorine-free waterproofing agents, making the surface tension of the nylon four-way stretch base fabric much lower than that of water. This change in surface energy forms a hydrophobic barrier layer on the fiber surface, causing water droplets to roll off the fabric surface in a spherical shape and prevent them from spreading and wetting, thus preventing the formation of a water film on the fabric surface. This not only reduces the weight gain from water absorption, but more importantly, it avoids blocking the breathability channels of the TPU waterproof and breathable membrane due to the surface water film, thereby solving the problem of a sharp decline in the breathability of the composite fabric under continuous rain conditions, maintaining dry and comfortable long-lasting protection even in harsh weather.

[0058] Secondly, in this invention, through step M1, thermoplastic polyurethane resin chips are mixed with hydrophilic modifiers, compatibilizers, antioxidants, and opening agents in a certain proportion, and reactive extrusion and granulation are carried out using a twin-screw extruder. The high shear force of the twin screw and the activation energy provided by the reactive extrusion process promote the chemical grafting or block copolymerization reaction between the active segments of the hydrophilic modifier and the thermoplastic polyurethane matrix. At the same time, the compatibilizer is used to reduce the interfacial tension between the hydrophilic component and the hydrophobic matrix to suppress macroscopic phase separation, and the antioxidant is used to capture free radicals to block the thermo-oxidative degradation chain reaction under high temperature shear. This achieves uniform molecular-level dispersion and chemical bonding of hydrophilic structural units in the polyurethane macromolecular network, forming a stable hydrophilic-hydrophobic microphase separation structure. The transport mode of water molecules is transformed into adsorption-diffusion-desorption based on chemical potential difference. While giving the masterbatch a highly efficient moisture-permeable function, the original mechanical strength and processing stability of the TPU matrix are preserved to the maximum extent.

[0059] In step M2, the hydrophilic modified TPU masterbatch is dehumidified and dried before being added to the casting unit. The melt is conveyed under stable pressure, extruded through a T-die, and cast onto a quenching roller for cooling and shaping. Deep dehumidification and drying remove trace amounts of moisture adsorbed inside the masterbatch, preventing hydrolysis and chain scission reactions that may occur during the high-temperature melting process of polyurethane molecules. Stable pressure conveying eliminates pressure pulsations and flow fluctuations during the melt rheological process. An opening agent is used to create micro-roughness on the surface of the film after quenching and shaping, achieving precise control over the stability of polymer molecular weight and the micron-level thickness uniformity of the film during film formation. This reduces the surface friction coefficient of the film. The resulting TPU waterproof and breathable film has a dense physical structure without pinhole defects and excellent anti-adhesion and slip properties, which helps the film maintain stable high hydrostatic pressure resistance and processing toughness suitable for low-tension composites even at extremely thin thicknesses.

[0060] Third, regarding the process parameters and formulation ratios of steps M11 and M12, simple physical blending is insufficient to address the compatibility issues between the polyether-based hydrophilic modifier and the polyester-based TPU matrix caused by polarity differences during the preparation of hydrophilic modified TPU masterbatch. A reaction temperature window of 180℃-200℃ is employed. This temperature range falls within the viscous flow zone of MDI-based polyester-based TPU and provides the activation energy required for transesterification or grafting reactions between polymer segments, while avoiding degradation of the polyurethane hard segments due to excessively high temperatures. Combined with high-speed screw shearing at 300r / min-500r / min, the strong mechanical shearing force forcibly disperses the high-viscosity TPU melt and the low-viscosity hydrophilic modifier, breaking down the interfacial tension barrier and increasing the reaction contact area.

[0061] Regarding component synergy, 15-25 parts of hydrophilic modifier is the threshold for constructing continuous moisture-permeable channels, while 3-5 parts of compatibilizer are key to stabilizing the system. Too much will reduce the strength of the main network, while too little will fail to suppress precipitation. Therefore, by using a specific reactive extrusion process and a specific ratio, in-situ chemical reactions or the formation of physically interlocking structures are promoted within the system, solving the technical problem of high-content hydrophilic components easily agglomerating and precipitating in the matrix, leading to a decrease in mechanical properties.

[0062] Fourth, through step M21, the hydrophilic modified TPU masterbatch contains a large number of polar hydrophilic groups and urethane bonds, exhibiting extremely strong hygroscopicity. Under melt processing conditions of 205℃-215℃, even trace amounts of water will act as nucleophiles to attack urethane bonds, initiating irreversible hydrolytic chain-severing reactions. This leads to a decrease in the average molecular weight of the polymer, a reduction in melt strength, and a tendency for bubbles, embrittlement, and loss of water pressure resistance after film formation. Therefore, by setting a temperature of 100℃-110℃ combined with a dew point temperature below -40℃ and vacuum drying, a high-temperature, low-partial-pressure devolatilization environment is created. This forces physically adsorbed water and some bound water to migrate deeply from the polymer matrix and drain, controlling the moisture content below the critical threshold of 0.02%. This ensures the integrity of the polyurethane main chain in subsequent processing at the chemical structure level.

[0063] In step M22, single-screw extruders often experience pressure fluctuations during melt delivery, which is detrimental to the preparation of 0.015mm-0.020mm films. Even small pressure fluctuations can lead to significant longitudinal thickness differences, with the thinnest point being the point of failure in water pressure resistance. The melt gear pump, as a volumetric conveying element, utilizes the precise metering characteristics of its gear meshing to isolate the extruder's pressure fluctuations, achieving constant pressure and flow feed to the T-die. Combined with die temperature control at 205℃-215℃, this ensures the melt is in an optimal viscous flow state, providing sufficient fluidity to form a continuous curtain while avoiding oxidative degradation due to excessive temperature.

[0064] Through step M23, TPU is a multi-block copolymer composed of hard and soft segments. The melt, heated to over 200°C, is contacted with a quenching roller at 15°C-25°C; this extreme supercooling provides an extremely high nucleation rate. This rapid cooling and crystallization inhibits the overgrowth and maturation of hard-segment spherulites, freezing the microphase separation structure and resulting in a film with a denser amorphous region structure and finer crystal domains. Combined with precise control of the casting speed, micron-level thickness of the film is physically achieved. While ensuring the film's physical barrier properties, controlling the thickness within 0.015mm-0.020mm maximizes the diffusion flux of water molecules, enabling the TPU waterproof and breathable film to possess excellent hydrostatic pressure resistance while exhibiting low moisture permeability.

[0065] Fifth, through step S31, the nylon four-way stretch base fabric has an extremely high elongation at break. If conventional low-modulus adhesives are used, when the fabric is subjected to significant stretching, the adhesive dots will peel off at the interface because they cannot follow the deformation of the base fabric, or the adhesive layer will break brittlely. A reactive polyurethane hot melt adhesive with an elongation at break greater than 500% is selected. Utilizing the high elastic recovery force provided by its long-chain molecular structure, the reactive polyurethane hot melt adhesive exhibits ultra-high extensibility similar to rubber after curing. Combined with a discontinuous dot-matrix pattern coating method, the adhesive dots form independent stress-dispersing units at the microscopic level, rather than a continuous rigid film layer. This not only avoids the adhesive layer restricting the elastic deformation of the base fabric, but also, by controlling the adhesive application amount to 10g / m² to 20g / m², ensures sufficient peel strength while preventing excessive adhesive penetration that could lead to hardening of the feel or blockage of the breathable channels.

[0066] In step S32, during the lamination process, the highly elastic nylon four-way stretch base fabric is extremely sensitive to tension. If laminated with a non-stretchable TPU film under tension, once the external force is removed, the elastic recoil force of the base fabric will generate huge interlayer shear stress, leading to edge curling, bubbling, or even delamination of the composite fabric. By controlling the overfeed rate to 2%-5%, more base fabric than the theoretical length is actively fed into the lamination zone, forcibly counteracting the traction tension during mechanical transmission and ensuring that the base fabric contacts the TPU film in a relaxed state without elastic elongation. This zero-stress lamination process eliminates potential residual stress between layers, allowing the three layers to achieve mechanical equilibrium in a natural state.

[0067] In step S33, the initial bonding of the reactive polyurethane hot melt adhesive relies on physical cooling and curing, but its final strength depends on chemical cross-linking. Under specific conditions of 40℃-50℃ and 24-48 hours, the isocyanate groups in the adhesive layer undergo chain extension and cross-linking reactions with moisture in the environment or substrate, transforming linear molecular chains into a three-dimensional network structure. This process not only significantly improves the heat resistance and hydrolysis resistance of the adhesive layer but also locks in the interlayer structure during lamination, preventing dimensional deformation due to subsequent thermal shrinkage or stress release. The composite fabric maintains extremely high peel strength and aging resistance during subsequent high-temperature washing and use in harsh environments. Attached Figure Description

[0068] Figure 1 This is the overall process flow diagram;

[0069] Figure 2 This is a flowchart of TPU film preparation;

[0070] Figure 3 This is a flowchart of the dot-matrix composite process;

[0071] Figure 4 This is a flowchart of the surface functionalization process. Detailed Implementation

[0072] The technical solution of the present invention will be further described in detail below with reference to the embodiments. Unless otherwise specified, the raw materials used in the following embodiments are all commercially available products.

[0073] I. Examples of preparation of raw materials and intermediates;

[0074] In the preparation of the composite fabric of the present invention, the TPU waterproof and breathable film needs to be prepared in advance, and the specific process is as follows.

[0075] Preparation Example 1: Hydrophilic modified TPU film A;

[0076] Step M1: Preparation of hydrophilic modified TPU masterbatch;

[0077] By weight, 100 parts of thermoplastic polyurethane resin chips (MDI-based polyester TPU, Shore A90 hardness), 20 parts of hydrophilic modifier (polyethylene glycol PEG with a molecular weight of 4000), 4 parts of compatibilizer (TPU-PEG block copolymer), 1 part of antioxidant (hindered phenolic antioxidant 1010), and 2 parts of opening agent (porous silica micropowder with a particle size of 3μm) were added to a high-speed mixer and mixed at 35°C for 15 minutes to obtain a premix.

[0078] The premixed material was added to a twin-screw extruder and subjected to high-shear reactive extrusion at a temperature of 190℃ and a screw speed of 400 r / min. During this process, the high shear force promotes the grafting reaction between the hydrophilic segments of PEG and the TPU matrix. The extruded material was then stretched and pelletized to obtain hydrophilic modified TPU masterbatch.

[0079] Step M2: Casting and film formation;

[0080] Raw material drying (M21): The hydrophilic modified TPU masterbatch prepared above was placed in a vacuum dryer, and the drying temperature was set to 105℃, while the ambient dew point temperature was controlled at -45℃, for continuous drying for 4 hours. The moisture content of the dried masterbatch was measured using a Karl Fischer moisture analyzer, and was found to be 0.015% (meeting the requirement of <0.02%), ensuring that hydrolytic degradation would not occur during subsequent processing.

[0081] Regulated melt extrusion (M22): The dried masterbatch is fed into a single-screw extruder for melting. The melt is precisely metered and pressure-regulated by a melt gear pump (eliminating pressure pulsation) before entering the T-die. The T-die temperature is controlled at 210℃ to extrude the melt in a curtain shape.

[0082] Casting and setting (M23): The melt is cast onto a quenching roller with a surface temperature of 20°C for rapid cooling and crystallization. By controlling the casting speed, a TPU waterproof and breathable film A with a thickness of 0.015 mm is obtained by winding.

[0083] Preparation Example 2: Hydrophilic Modified TPU Film B;

[0084] The only difference from Preparation Example 1 is the minor adjustments to the formulation and process:

[0085] Masterbatch preparation: 100 parts MDI-based polyester TPU (Shore A85), 15 parts hydrophilic modifier (polyethylene oxide PEO with a molecular weight of 6000), 3 parts compatibilizer (maleic anhydride-grafted TPU), 0.5 parts antioxidant, and 1 part opening agent. Twin-screw extruder temperature 180℃, rotation speed 300 r / min.

[0086] Casting: Drying temperature 100℃, dew point -40℃, drying time 5h. Moisture content was measured to be 0.019%. T-die temperature 205℃, quench roller temperature 15℃. A TPU waterproof and breathable film B with a thickness of 0.020mm was obtained.

[0087] Preparation Example 3: Hydrophilic Modified TPU Film C;

[0088] The only difference from Preparation Example 1 is that:

[0089] Masterbatch preparation: 100 parts MDI-based polyester TPU (ShoreA95), 25 parts hydrophilic modifier (PEG4000), 5 parts compatibilizer (TPU-PEG block copolymer), 1.5 parts antioxidant, and 3 parts opening agent. Twin-screw extruder temperature 200℃, speed 500 r / min.

[0090] Casting: Drying temperature 110℃, dew point -50℃, drying time 3h. Moisture content was measured at 0.012%. T-die temperature 215℃, quench roller temperature 25℃. A TPU waterproof and breathable film C with a thickness of 0.018mm was obtained.

[0091] II. Implementation Examples

[0092] Example 1;

[0093] A method for preparing a wear-resistant and waterproof composite fleece-lined fabric includes the following steps:

[0094] Step S1: Prepare nylon four-sided elastic base fabric;

[0095] The raw materials consist of 86% nylon yarn and 14% spandex yarn by weight. The nylon yarn is 40D / 36F semi-dull stretch textured yarn (SDDTY), and the spandex yarn is 20D. A two-way elastic nylon four-way stretch base fabric is produced through an interlacing process.

[0096] Step S2: Prepare the thermal insulation inner layer;

[0097] Select a base fabric with a weight of 180g / m² and perform a single-brush, single-shake pile-raising process on it to form a pile layer on one side and a smooth bonding surface on the other side.

[0098] Step S3: Dot-like compounding;

[0099] Preparation: Select the TPU waterproof and breathable film A prepared in Example 1. Select a reactive polyurethane (PUR) hot melt adhesive (model: JCC-PUR) with an elongation at break of 600% and heat it to 110°C to melt.

[0100] S31 Coating: Transfer coating is performed using a gravure roller with a dot matrix pattern engraved on the surface. Molten hot melt adhesive is applied to the inner surface of the nylon four-way elastic base fabric in a discontinuous dot pattern, and the amount of adhesive applied is controlled to be 15g / m².

[0101] S32 lamination: During the open time of the hot melt adhesive, the TPU film and the thermal insulation inner layer are introduced into the composite unit. The overfeed rate of the nylon four-way stretch base fabric is set to 3% through the overfeed device at the fabric inlet.

[0102] State Observation and Confirmation: Under this overfeed setting, it was observed that the nylon four-way stretch base fabric was in a relaxed, drooping state in the area before entering the constant temperature pressure roller (50℃), and neither the warp nor the weft directions were in a taut, stretched state, i.e., it was in a state where no elastic elongation had occurred. In this state, the nylon four-way stretch base fabric, TPU waterproof and breathable film, and thermal insulation inner layer were laminated into a single structure by the pressure roller.

[0103] Microstructure: Microscopic observation shows that the composite interface is connected by discontinuous adhesive dots, and microporous channels for moisture to penetrate are retained between the adhesive dots; and when the fabric is stretched, the high-elastic adhesive dots deform synchronously with the base fabric, forming an elastic buffer layer.

[0104] S33 curing: The coil is wound up and left to cure at 45°C for 36 hours to complete the cross-linking and curing process.

[0105] Step S4: Surface functionalization treatment;

[0106] S41 Solution Preparation: A waterproofing working solution is prepared using water as the medium. It contains 40 g / L of C6 organic fluorine waterproofing agent and 10 g / L of blocked isocyanate crosslinking agent (the end-capping agent is methyl ethyl ketone oxime, with an unsealing temperature of approximately 130℃-140℃). The pH is adjusted to 5.0 with acetic acid.

[0107] S42 padding: The composite fabric is padded, and the roll-off rate is controlled at 70%.

[0108] S43 Curing: The product is fed into a setting machine. First, it is pre-dried at 110°C to remove moisture; then it is baked at 165°C for 60 seconds. At this temperature, the blocked isocyanate crosslinking agent is completely deblocked, and the released isocyanate groups react with the fiber surface and the waterproofing agent to form a durable network film structure.

[0109] Example 2;

[0110] The difference from Example 1 lies in the adjustment of process parameters:

[0111] Film: The TPU film B prepared in Example 2 was selected.

[0112] Composite: PUR hot melt adhesive with an elongation at break of 550% and an application rate of 10 g / m². With an overfeed rate of 2% for the nylon four-way stretch base fabric, the base fabric was observed to be in a relaxed state without elastic elongation. Curing conditions: 40℃, 48 h.

[0113] DWR treatment: The waterproofing solution contains 20g / L of fluorine-free waterproofing agent and 5g / L of blocked isocyanate crosslinking agent (unsealing temperature 140℃), pH 4.0. Baking conditions: pre-baking at 100℃, curing at 160℃ for 90 seconds.

[0114] Example 3;

[0115] The difference from Example 1 lies in the adjustment of process parameters:

[0116] Film: The TPU film C prepared in Example 3 was selected.

[0117] Composite: PUR hot melt adhesive with an elongation at break of 700% and an application rate of 20 g / m². With an overfeed rate of 5% for the nylon four-way stretch base fabric, the base fabric was observed to be in a relaxed state without elastic elongation. Curing conditions: 50℃, 24 h.

[0118] DWR treatment: The waterproofing solution contains 60g / L of organic fluorine waterproofing agent and 15g / L of blocked isocyanate crosslinking agent (unsealing temperature 130℃), pH 6.0. Baking conditions: pre-baking at 120℃, curing at 170℃ for 45 seconds.

[0119] III. Comparative Examples;

[0120] Comparative Example 1;

[0121] The only difference from Example 1 is that the TPU film used in step S3 is a commercially available ordinary TPU film (without hydrophilic modifiers and compatibilizers, and without reactive extrusion).

[0122] Comparative Example 2;

[0123] The only difference from Example 1 is that in step S32, overfeeding is not set (overfeed rate 0%), but the base fabric is pulled into the composite zone by a conventional tension roller, and it is observed that the base fabric is in a taut and stretched state (tension of about 30N) before entering the pressure roller. The rest is the same as in Example 1.

[0124] Comparative Example 3;

[0125] The only difference from Example 1 is that in step S31, ordinary PUR hot melt adhesive with an elongation at break of 200% is used. The rest is the same as in Example 1.

[0126] Comparative Example 4;

[0127] The only difference from Example 1 is that no blocked isocyanate crosslinking agent was added to the waterproofing working solution in step S41. Everything else is the same as in Example 1.

[0128] IV. Performance testing;

[0129] The fabrics prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to performance tests, and the results are shown in Table 1.

[0130] Hydrostatic pressure resistance: AATCC127 standard.

[0131] Moisture permeability: GB / T12704.2-2009, the higher the value, the better the breathability.

[0132] Abrasion resistance: GB / T21196.2-2007.

[0133] Peel strength: ASTM D903 standard.

[0134] Surface moisture resistance: GB / T4745-2012 standard, the level was tested before the initial wash and after 20 washes.

[0135] Overall color fastness: including resistance to dry rubbing (GB / T 3920-2008), resistance to perspiration (GB / T 3922-2013), and resistance to water (GB / T 5713-2013).

[0136] Ecological safety indicators: Formaldehyde, pH value and odor are tested according to GB 18401-2010 (Class B, direct contact with skin).

[0137] Table 1: Performance Test Results;

[0138] project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 <![CDATA[Hydrostatic pressure resistance (mmH2O)]]> >10000 >10000 >10000 >10000 >10000 >10000 >10000 Moisture permeability (g / (m²·24h)) 4300 4100 4500 800 4150 4200 4300 Abrasion resistance (times) >50000 >50000 >50000 >50000 15000 >50000 >50000 Initial peel strength (N / 2.5cm) 18.2 17.5 18.8 15.6 12.1 16.5 18.0 Peel strength (N / 2.5cm) after 20 washes 16.8 16.1 17.5 14.2 10.5 11.2 16.5 warp elongation (%) 35.5 34.2 36.8 35.0 18.4 20.1 35.5 Finished product weight (g / m²) 295 285 310 295 295 295 295 Initial surface moisture resistance (grade) 4-5 4-5 4-5 4-5 4-5 4-5 4-5 Surface moisture resistance (grade) after 20 washes 4-5 4-5 4-5 4-5 4-5 4-5 1-2 Overall colorfastness (grade) 4-5 4-5 4-5 3-4 3-4 4-5 3-4 Formaldehyde and carcinogenic aromatic amines Not detected Not detected Not detected Not detected Not detected Not detected Not detected pH value / odor 6.6 / None 6.5 / None 6.8 / None 6.7 / None 6.6 / None 6.6 / None 6.6 / None feel and appearance Soft and smooth Soft and smooth Soft and smooth harder curled edges, stiff There is an abnormal noise when stretching. soft

[0139] Results analysis:

[0140] The finished product weights of Examples 1-3 were all controlled within 310 g / m², achieving excellent lightweighting compared to traditional composite fabrics. Simultaneously, thanks to the synergistic effect of the overfeed process and the high-elasticity PUR adhesive, the warp elongation of the fabrics in these examples reached over 35%, while the elongation of Comparative Example 2 (which did not use overfeed) and Comparative Example 3 (which used low-elasticity adhesive) decreased significantly to around 20%. This demonstrates that the present invention perfectly preserves the four-sided high-elasticity properties of the fabric while achieving lightweighting, and maintains high peel strength even after 20 washes, solving the technical pain points of composite fabrics being prone to stiffening and not washable.

[0141] Comparative Example 1 used a regular TPU membrane with a moisture permeability of only 800 g / (m²·24h), exhibiting extremely poor air permeability. Example 1, through the hydrophilic modification process of Example 1, significantly increased the moisture permeability to 4300 g / (m²·24h) while maintaining water pressure resistance (>10000), achieving a balance between high waterproofness and high moisture permeability.

[0142] Comparative Example 2, when laminated under tension, showed a significant decrease in peel strength (12.1 N) and severe edge curling in the finished product. Example 1, by setting a 3% overfeed rate, achieved relaxed lamination without elastic elongation, effectively eliminating interlayer stress and ensuring high peel strength (18.2 N) and dimensional stability.

[0143] Comparative Example 3 used a low-elasticity adhesive, which, although having acceptable peel strength, resulted in brittle fracture of the adhesive layer (with abnormal noise) when the fabric was stretched. Example 1 used a high-elasticity adhesive with an elongation at break of 600%, which constructed an elastic cushioning layer with better feel and resilience.

[0144] Comparative Example 4, without crosslinking agent, showed a sharp drop in surface moisture resistance to level 1-2 after 20 washes. Example 1, with the addition of a blocked isocyanate crosslinking agent and deblocking and curing at high temperature, maintained excellent surface moisture resistance of level 4-5 after 20 washes, strongly demonstrating the wash durability of the DWR process.

[0145] The surface layer of Examples 1-3 adopts a nylon four-way stretch interwoven structure. After Martindale test, its abrasion resistance exceeded 50,000 cycles, which verified the high strength and abrasion resistance of the composite fabric in harsh outdoor environments.

[0146] The above embodiments are merely explanations of the present invention and are not intended to limit the present invention. After reading this specification, those skilled in the art can make modifications to these embodiments without contributing any inventive step, but as long as they are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. A method for preparing a wear-resistant and waterproof composite fleece-lined fabric, characterized in that, Includes the following steps: Step S1: Prepare nylon four-sided elastic base fabric; Nylon yarn and spandex yarn are selected as raw materials and nylon four-way elastic base fabric with warp and weft elasticity is made by interlacing process; Step S2: Prepare the thermal insulation inner layer; Select a base fabric and perform a single-brush, single-shake napping process on it to form a nap layer on one side and a smooth bonding surface on the other side. Step S3: Dot-like compounding; Select a TPU waterproof and breathable film and place it between the inner surface of the nylon four-way elastic base fabric and the bonding surface of the thermal insulation inner layer. The method employs dot bonding, utilizing reactive polyurethane hot melt adhesive with a discontinuous dot distribution. Under conditions of overfeeding and no elastic elongation in the warp and weft directions, the nylon four-way stretch base fabric, TPU waterproof and breathable film, and thermal insulation inner layer are laminated into a single structure. Dot bonding achieves lamination while simultaneously constructing an elastic buffer layer through discontinuous adhesive dots, and retains microporous channels for moisture penetration and elastic deformation space for the fabric under stress in the un-adhesive areas. Step S4: Surface functionalization treatment; The outer surface of the composite nylon four-way elastic base fabric is treated with DWR for durability and water repellency.

2. The method for preparing the wear-resistant and waterproof composite fleece-lined fabric according to claim 1, characterized in that: In step S3, the TPU waterproof and breathable film is a hydrophilic modified non-porous polyurethane film, and the preparation process includes the following steps: Step M1: Preparation of modified masterbatch; Thermoplastic polyurethane resin chips are mixed with hydrophilic modifier, compatibilizer, antioxidant and opening agent in a certain proportion, and then reacted and granulated through a twin-screw extruder to obtain hydrophilic modified TPU masterbatch. Step M2: Casting and film formation; After being dehumidified and dried, the hydrophilic modified TPU masterbatch is added to the casting machine. The melt is conveyed under stable pressure and extruded through a T-die. It is then cast onto a cooling roller for cooling and shaping. After edge trimming, thickness measurement, and winding, a TPU waterproof and breathable film is obtained.

3. The method for preparing the wear-resistant and waterproof composite fleece-lined fabric according to claim 2, characterized in that: Step M1 includes the following sub-steps: Step M11: Mixing; By weight, 100 parts of thermoplastic polyurethane resin chips, 15-25 parts of hydrophilic modifier, 3-5 parts of compatibilizer, 0.5-1.5 parts of antioxidant, and 1-3 parts of opening agent are added to a high-speed mixer and mixed at 30℃-40℃ for 10-20 minutes to obtain a premix. Step M12, reaction extrusion; The premixed material is added to a twin-screw extruder and reacted and blended at a temperature of 180℃-200℃ and a screw speed of 300r / min-500r / min. The mixture is then extruded into strands, granulated, and dried to obtain hydrophilic modified TPU masterbatch.

4. The method for preparing the wear-resistant and waterproof composite fleece-lined fabric according to claim 3, characterized in that: The thermoplastic polyurethane resin chips are MDI-based polyester TPU; the hydrophilic modifier is polyethylene glycol or polyethylene oxide with a molecular weight of 4000-6000; the compatibilizer is TPU-PEG block copolymer or maleic anhydride-grafted TPU; and the opening agent is porous silica micropowder with a particle size of 2μm-5μm.

5. The method for preparing the wear-resistant and waterproof composite fleece-lined fabric according to claim 2, characterized in that: Step M2 includes the following sub-steps: Step M21: Raw material drying; The hydrophilic modified TPU masterbatch is vacuum dried at 100℃-110℃ and dew point temperature below -40℃ for 3h-5h, so that the moisture content of the hydrophilic modified TPU masterbatch is less than 0.02%; Step M22, stabilizing melt extrusion: The dried masterbatch is transported to a single screw extruder for melting. After the melt is stabilized by a melt gear pump, it enters the T-die. The temperature of the T-die is controlled at 205℃-215℃, so that the melt is extruded in a curtain shape. Step M23: Casting and setting; The surface temperature of the quenching roller is controlled at 15℃-25℃, so that the extruded melt can be rapidly cooled and crystallized on the quenching roller. By controlling the casting speed, the thickness of the formed TPU waterproof and breathable film is 0.015mm-0.020mm.

6. The method for preparing the wear-resistant and waterproof composite fleece-lined fabric according to claim 1, characterized in that: In step S1, the raw materials of the nylon four-way stretch base fabric include 86% nylon yarn and 14% spandex yarn by weight percentage, wherein the nylon yarn has a yarn count of 40D. In step S2, the base fabric is a fleece base fabric with a weight of 180 g / m². 2 .

7. The method for preparing the wear-resistant and waterproof composite fleece-lined fabric according to claim 1, characterized in that: Step S3 includes the following sub-steps: Step S31: Hot melt adhesive dot transfer coating; A reactive polyurethane hot melt adhesive with an elongation at break greater than 500% was selected as the adhesive. The reactive polyurethane hot melt adhesive was heated and melted. A gravure roller with a dot matrix pattern engraved on the surface was used for transfer coating. The molten hot melt adhesive was applied to the inner surface of the nylon four-way elastic base fabric in a discontinuous dot pattern. The amount of adhesive applied was controlled to be 10g / m² to 20g / m². Step S32: Three-layer pressure lamination; During the open time of the hot melt adhesive, the TPU waterproof and breathable film and the thermal insulation inner layer are introduced, and the overfeed rate of the nylon four-way elastic base fabric is controlled at 2%-5%, so that the nylon four-way elastic base fabric enters the composite area without elastic elongation. The three-layer materials are then laminated under pressure by a constant temperature pressure roller. Step S33: Maturation and shaping; The laminated fabric is rolled up and left to stand at 40°C to 50°C for 24 to 48 hours to allow the reactive polyurethane hot melt adhesive to complete cross-linking and curing.

8. The method for preparing the wear-resistant and waterproof composite fleece-lined fabric according to claim 1, characterized in that: Step S4 includes the following sub-steps: Step S41: Preparation of waterproofing working solution; Using water as a medium, prepare a waterproof working solution containing 20g / L-60g / L of organic fluorine waterproofing agent or fluorine-free waterproofing agent and 5g / L-15g / L of blocked isocyanate crosslinking agent, and adjust the pH value of the working solution to 4.0-6.

0. Step S42: Immersion in liquid; The composite fabric is immersed in the waterproof working liquid, and then the liquid is applied by a uniform rolling mill, with the residual rate controlled at 60%-80%, so that the waterproof working liquid is evenly attached to the surface of the fabric fibers. Step S43: High-temperature baking and curing; The impregnated fabric is fed into a setting machine and treated using a segmented temperature control method. First, it is pre-dried at 100℃-120℃ to remove moisture from the fabric surface. Then, it is baked and cured at 160℃-170℃ for 45-90 seconds to allow the waterproofing agent to form a cross-linked film structure on the fiber surface.

9. The method for preparing the wear-resistant and waterproof composite fleece-lined fabric according to claim 1, characterized in that: In step S1, the yarn structure of the nylon four-way stretch base fabric is as follows: both the warp and weft directions are made of semi-dull stretch textured yarn with a specification of 40D / 36F and 20D spandex yarn, which are interwoven together.

10. A wear-resistant and waterproof composite fleece-lined fabric, characterized in that: It is prepared by any one of the preparation methods described in claims 1 to 9.

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