Anti-mosquito fabric base material resin as well as preparation method and application thereof

Abstract

The invention relates to an anti-mosquito fabric base material resin which comprises the following components in parts by mass: UHMWPE (Ultra High Molecular Weight Polyethylene) resin; hDPE (high-density polyethylene); a mosquito repellent microcapsule; a compatilizer; an antioxidant; a spinning aid; and the anti-mosquito resin comprises a cinnamomum camphora leaf essential oil derivative. The invention also provides a preparation method and application of the anti-mosquito fabric base material resin. According to the anti-mosquito fabric base material resin as well as the preparation method and the application thereof, the UHMWPE high-strength base material is combined with microcapsule long-acting loading, and integrated process combination is adopted, so that quadruple balance of efficient and lasting mosquito repelling, excellent mechanical property, comfortable and safe wearing and flexible and adaptive scene can be realized; and the method is particularly suitable for the fields of high-end outdoor products, children products, professional protection and the like with high requirements on quality and safety, and has remarkable market differentiation competitiveness.

Description

Technical Field

[0001] This invention belongs to the field of special fabrics, and particularly relates to mosquito-repellent fabrics, specifically to the substrate resin of mosquito-repellent fabrics, its preparation method and application. Background Technology

[0002] Mosquitoes are the primary vectors for diseases such as dengue fever, malaria, and Japanese encephalitis. In 2024, the number of dengue fever cases worldwide exceeded one million, with over 700,000 deaths annually due to mosquito-borne diseases, resulting in economic losses of $3 billion (Aedes mosquitoes only). Traditional chemical mosquito repellents (such as DEET) pose problems such as skin irritation and environmental pollution, necessitating safer protective measures. Furthermore, outdoor workers in forestry, agriculture, and the military face high-density mosquito bites (up to hundreds per cubic meter). Ordinary clothing, with its large pores, allows mosquitoes to easily penetrate; thicker clothing reduces breathability, making it prone to heat stress in summer.

[0003] Currently available mosquito-repellent technologies include: insect repellent soaking, surface finishing, and blending spinning. While these technologies have made significant progress in mosquito repellency, in-depth analysis reveals existing problems. Several mosquito-repellent fabrics share some common issues: The mosquito-repellent properties of existing mosquito-repellent fabrics are insufficient in terms of durability and washability, and most technical solutions struggle to achieve both immediate and long-term mosquito-repellent effects. Fabrics prepared by soaking in mosquito repellent agents can initially achieve a repellency rate of over 85%, but this rate drops sharply to 40%–60% after five standard washes. Furthermore, the manufacturing process of traditional mosquito-repellent fabrics involves various environmental pollutants. The bioaccumulation of synthetic mosquito repellents (such as permethrin) poses ecological risks; experiments show that the 48h-LC50 of permethrin-containing fabric washing solutions against aquatic organisms (Daphnia magna) is only 0.15 mg / L. To achieve long-lasting mosquito repellency, existing technologies often sacrifice comfort. Multi-layered composite fabrics are 0.8–1.5 mm thick, with an air permeability of less than 30 cm³ / s / cm² (summer clothing requires >50 cm³ / s / cm²), leading to the risk of heat stress. Existing mosquito-repellent fabrics often suffer from limitations such as single-function design and sacrificing performance for effectiveness, resulting in problems like good mosquito repellency but lack of durability, or durability but lack of comfort. Summary of the Invention

[0004] The main objective of this invention is to address the above-mentioned problems by providing a mosquito-repellent fabric substrate resin, its preparation method, and its application.

[0005] The purpose of this invention is to provide a resin for a mosquito-repellent fabric substrate, characterized in that, by weight, the substrate resin comprises the following components: UHMWPE resin 50%–70%; HDPE 20%~40%; Mosquito repellent microcapsules 2%–6%; Compatibilizer 0.5%–3%; Antioxidant 0.2%–2%; Spinning aids 1%–3%; The mosquito repellent resin contains 5% to 8% of camphor leaf essential oil derivatives.

[0006] Preferably, the molecular weight of the UHMWPE resin is 1.5 million to 2 million.

[0007] Preferably, the molecular weight of the HDPE is 300,000 to 500,000.

[0008] Preferably, the particle size of the mosquito-repellent microcapsules is 5-20 μm, and the core material of the mosquito-repellent microcapsules is the active substance permethrin, wherein the active substance permethrin accounts for 20%-40% of the mass percentage of the mosquito-repellent microcapsules. The camphor leaf essential oil derivative accounts for 3% to 8% of the mass of the mosquito repellent resin.

[0009] Preferably, the compatibilizer is maleic anhydride-grafted PE with a grafting rate ≥1.2%; the antioxidant is a pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] 1010 / tris(2,4-di-tert-butylphenyl) phosphite 168 composite agent; and the spinning aid is calcium stearate and polyethylene glycol.

[0010] This invention also provides a method for preparing the resin used as the substrate for the mosquito-repellent fabric, characterized in that the preparation method includes the following steps: Premixing: UHMWPE resin and HDPE are added to a mixer for premixing; Additive mixing: Add compatibilizer, antioxidant, and spinning auxiliaries, heat to 70℃~90℃ and stir; Functional ingredient mixing: Add mosquito repellent microcapsules and mosquito-repellent resin, and stir; Melt blending: The mixture is fed into a twin-screw extruder with the following temperatures: feeding section 130℃~150℃, melting section 190℃~210℃, mixing section 200℃~220℃, homogenization section 180℃~200℃, die head 185℃~205℃, screw speed 350~450rpm, and feeding speed 20~30kg / h. The extrudate is water-cooled at 20-30℃, drawn, and pelletized to a particle size of 3-5mm, and then vacuum-dried at 70-90℃.

[0011] Preferably, the stirring speed for adding the mosquito-repellent microcapsules and mosquito-repellent resin is 300-400 rpm.

[0012] The present invention also provides the application of the aforementioned mosquito-repellent fabric substrate resin in mosquito-repellent fabrics.

[0013] Preferably, the mosquito-repellent fabric substrate resin is first spun by melt spinning and then woven.

[0014] The mosquito repellent fabric substrate resin, its preparation method, and its application of the present invention utilize a UHMWPE high-strength substrate combined with long-lasting microcapsule loading and an integrated process combination to achieve a four-fold balance of high-efficiency and long-lasting mosquito repellency, excellent mechanical properties, comfortable and safe wear, and flexible adaptation to various scenarios. It is especially suitable for high-end outdoor, children's products, and professional protective fields with high requirements for quality and safety, and has significant market differentiation competitiveness. Attached Figure Description

[0015] Figure 1 This is a test report image of the mosquito-repellent fabric of the present invention. Detailed Implementation

[0016] To provide a clearer understanding of the technical content of this invention, the following embodiments are provided in detail. However, it is important to note that these descriptions are merely for further illustrating the features and advantages of this invention, and not for limiting the scope of the claims.

[0017] Unless otherwise specified, the reagents and methods involved in the examples are all commonly used in the art.

[0018] Example 1 Raw material preparation UHMWPE resin (molecular weight 1.5 million to 2 million): provides high strength as a basic fiber raw material, and its molecular weight is suitable for spinning flow to avoid filament breakage.

[0019] High-density polyethylene (HDPE, molecular weight 300,000 to 500,000): Improves melt flowability and aids spinning; its proportion is higher than that of pure modified resin, thus improving processability.

[0020] Mosquito repellent microcapsules (particle size 5-20μm): The core mosquito repellent ingredient achieves long-lasting sustained release, and the particle size is matched to the spinning process to avoid clogging the spinneret holes.

[0021] The mosquito-repellent microcapsules were prepared by in-situ polymerization, and the specific steps are as follows: Emulsification and dispersion. The mosquito-repellent active substance (core material, permethrin) was added to the aqueous phase of distilled water. Under the action of the emulsifier polystyrene maleic anhydride copolymer, emulsification was carried out using a high-speed homogenizer at 12000 rpm. The addition ratio of permethrin, emulsifier, and polystyrene maleic anhydride copolymer was 3:1:1, forming a stable fine oil / water emulsion.

[0022] Prepolymerization and reaction of wall materials. Melamine, formaldehyde or their prepolymers, the raw materials for wall materials, are added to the above emulsion. The pH value is adjusted to acidic, usually 4 to 6. The mixture is heated at 300 to 600 rpm and heated to 60 to 80°C for 2 hours under moderate stirring speed. The wall material monomers are polymerized and cured on the surface of the core material droplets.

[0023] Post-processing. After the reaction, the mixture was cooled, filtered, washed, and dried at 50°C for 0.5 hours to obtain microcapsule powder. The actual encapsulation rate of the mosquito-repellent microcapsules after preparation was 75%, and the drug loading was 80%.

[0024] Compatibilizer (maleic anhydride-grafted PE, grafting rate ≥1.2%): enhances the interfacial bonding between resin and microcapsules, and improves dispersion stability during spinning.

[0025] Antioxidant (1010 / 168=1:2 composite): Prevents oxidative degradation of resin / fiber and is suitable for high-temperature spinning environments.

[0026] Spinning aid (calcium stearate + polyethylene glycol): mass ratio 1:3, reduces spinning friction, protects microcapsules, and reduces spinneret wear.

[0027] Mosquito-repellent resin (containing natural camphor leaf essential oil derivative): works synergistically with the microcapsule core material to enhance the longevity of mosquito repellency after washing.

[0028] The specific preparation method of the mosquito-repellent resin is as follows: Weighing and Premixing: Weigh out component A (methyl etherified melamine-formaldehyde resin) and component B (polyisocyanate curing agent) according to the instructions, in a mass ratio of 10:1, and pour them into two different cups. The key step is to add natural camphor powder to component A, at a rate of 3%–8% of the total resin mass. Stir slowly at room temperature until completely dissolved. If dissolving is slow, place the cups in warm water (water temperature <40℃) to aid dissolution.

[0029] Mixing the main agents: Pour the camphor-dissolved Agent A into the cup containing Agent B. Stir slowly and thoroughly in the same direction for 2-3 minutes, ensuring the liquid is evenly mixed on the sides and bottom of the cup. Avoid vigorous stirring to prevent introducing too many air bubbles.

[0030] Defoaming and Pouring: After mixing, let stand for 2-3 minutes to allow large air bubbles to rise naturally. Slowly pour the resin liquid into the mold. Quickly run a toothpick or lighter across the surface to eliminate small air bubbles.

[0031] After mixing, the resin is cured at a temperature of 100℃ for 2 hours. The cured mosquito-repellent resin has a soft feel and an adhesion of over 80%. After 20 water washes, the residual rate of key components is over 60%.

[0032] Premix: Put UHMWPE and HDPE into a high-speed mixer (800-1000 rpm) and premix at room temperature for 15 minutes; Additives mixing: Add compatibilizer, antioxidant, and spinning aid, heat to 80℃ and stir for 10 minutes; Mixing of functional ingredients: Add mosquito repellent microcapsules and mosquito-repellent resin, and stir at low speed (300-400 rpm) for 5 minutes to avoid breaking the microcapsules; Melt blending: The mixture is fed into a twin-screw extruder with the following temperatures: feeding section 130-150℃, melting section 190-210℃, mixing section 200-220℃, homogenizing section 180-200℃, die head 185-205℃, screw speed 350-450 rpm, and feeding speed 20-30 kg / h. Post-granulation treatment: The extrudate is water-cooled at 20-30℃, drawn, and granulated (particle size 3-5mm), and then vacuum-dried at 80℃ for 4 hours (moisture content ≤0.1%) for later use.

[0033] Mosquito-repellent UHMWPE fiber spinning: The process employs melt spinning, balancing production efficiency and microcapsule retention rate. The specific spinning steps are as follows: Raw material drying: Place the modified base resin particles into a vacuum drying oven and dry at 85°C for 6 hours; Melt extrusion: A single-screw spinning machine is used. Barrel temperatures are 140℃ in zone 1, 180℃ in zone 2, 200℃ in zone 3, and 210℃ in zone 4. The spinneret temperature is 205℃. The spinneret orifice diameter is 0.2–0.3 mm, and the number of orifices is 300–500. Screw diameter: 20 mm; L / D ratio: 16:1; Temperature control: ≤300℃, accuracy ±2℃; Power: 550 W; Material: Stainless steel / ceramic.

[0034] Cooling and forming: The cooling device is used to cool the air at a temperature of 25-30℃, a speed of 0.5-1m / s, and a distance of 15-20cm. Traction and stretching: A multi-stage traction machine is used, with a first-stage traction speed of 500-800 m / min, a second-stage stretching ratio of 5-8 times, and a stretching temperature of 100-120℃; Heat setting: Place in a heat setting oven at 120–140°C for 30–60 seconds; Winding: Using a winding machine, the winding speed is 2500~3500m / min and the winding tension is 5~10cN.

[0035] The specific performance indicators of the mosquito-repellent UHMWPE fiber are as follows: Linear density: 100~200D; Tensile strength: ≥15cN / dtex; Elongation at break: 15~25%; Microcapsule loading rate: ≥6%.

[0036] Preparation of mosquito-repellent UHMWPE fabric Preparation before weaving Pretreatment of mosquito-repellent UHMWPE fibers: The wound mosquito-repellent UHMWPE fibers are twisted into 2-3 strands and ≤0.5% antistatic oil is applied to reduce static electricity and friction during weaving; Warping process: A slit warping machine is used, with a warping speed of 200-300m / min, a warp density of 100-120 threads / inch for outdoor fabrics and 80-100 threads / inch for close-fitting fabrics, and a warping tension of 3-5cN.

[0037] Machine-woven fabric (suitable for outdoor tents, mosquito-proof jackets) Weaving equipment: air-jet loom or rapier loom Fabric structure: plain weave or twill weave Weaving parameters: weft density 80-100 yarns / inch, loom speed 300-400 rpm, shedding time 180-200° Finished product specifications: The prepared fabric is ultra-thin and lightweight, with a weight of 60g / m² and a thickness of 0.12mm. Knitted fabric (suitable for close-fitting mosquito-repellent clothing and gloves) Weaving equipment: Circular knitting machine (single-sided or double-sided) Fabric structure: plain knit or rib knit Weaving parameters: machine gauge 16-20 needles / inch, loop length 2.5-3.5mm, machine speed 200-300rpm. Finished product specifications: Weight 60g / m², thickness 0.2~0.3mm Post-weaving finishing Pre-shrinkage Woven fabrics: Pre-shrinking machine is used, temperature 80-90℃, humidity 60-70%, pre-shrinking rate 3-5%.

[0038] Knitted fabrics: Wash in a relaxed washing machine at ≤30℃ cold water, and air dry after spin-drying.

[0039] Functionality Reorganization (Optional) Waterproof and stain-resistant finishing: Impregnate with fluorocarbon resin finishing agent (5-10g / L, solid content 20%), roll dry (70% residue), and dry at 100-110℃ for 5 minutes. Enhanced mosquito repellent treatment: Soak in a 5-8 g / L mosquito repellent solution (same as the microcapsule core material) at room temperature for 10 minutes, then squeeze dry and dry at 60-70℃ for 10 minutes.

[0040] Shaping treatment Temperature: 110~130℃; Time: 3~5 minutes; Requirements: Uniform tension to ensure stable fabric dimensions and a smooth feel.

[0041] Example 2 Fabric basic performance testing Tensile strength (warp / weft): Referring to GB / T 3923.1, the qualified index of UHMWPE mosquito repellent fabric in Example 1 of this invention is ≥1000N / 5cm.

[0042] Elongation at break (warp / weft): According to GB / T 3923.1, the qualified index of UHMWPE mosquito repellent fabric in Example 1 of this invention is ≥15%.

[0043] Breathability: Referring to GB / T 5453, the UHMWPE mosquito repellent fabric in Example 1 of this invention has a breathability of ≥500mm / s for woven fabric and ≥800mm / s for knitted fabric.

[0044] Wash fastness: According to GB / T 3921, the UHMWPE mosquito repellent fabric in Example 1 of this invention showed no obvious pilling or deformation after 20 washes.

[0045] Friction fastness: Referring to GB / T 3920, the UHMWPE mosquito repellent fabric in Example 1 of this invention has a dry friction rating of ≥4 and a wet friction rating of ≥3.

[0046] The mosquito repellency test shall be conducted in accordance with GB / T 30126-2013 "Test and Evaluation of Mosquito Repellency Performance of Textiles".

[0047] Test environment: temperature 25±1℃, relative humidity 65±5%, no airflow interference, test cage volume 1m×1m×1m.

[0048] Test mosquitoes: 30 adult female Aedes albopictus mosquitoes that had emerged 4-7 days prior and had not yet fed on blood.

[0049] Test procedure: Cut a 15×15cm fabric sample, wash it three times at 30℃ for 5 minutes each time, and then air dry it; fix the sample on one side of the test cage, and place a blank cotton control sample on the other side; release mosquitoes and observe them continuously for 30 minutes after they have adapted for 10 minutes, and record the number of mosquitoes that land on the sample surface (N1) and the number of mosquitoes on the control sample surface (N0).

[0050] Test results: Mosquito repellency rate (%) = (N0 - N1) / N0 × 100%, such as Figure 1 As shown in the results of the four parallel experiments, the unwashed UHMWPE fabric achieved a repellency rate of up to 90% against Aedes albopictus, with an average of 84.8%, and a mosquito repellency rating of A, indicating a very strong repellency effect.

[0051] In Example 1 of this invention, the mosquito repellency rate of the UHMWPE mosquito-repellent fabric after washing is as follows: After 10 washes, the mosquito repellency rate of the UHMWPE fabric is still ≥75%, and the mosquito repellency rating is still A, indicating a very strong repellent effect.

[0052] The mosquito-repellent fabric substrate resin, its preparation method, and its application provided by this invention offer long-lasting and stable mosquito-repellent effects. Specifically, it boasts high mosquito-repellent efficiency, with a core mosquito-repellent rate of 84.8%, far exceeding most existing mosquito-repellent fabrics. Conventional products typically have a mosquito-repellent rate of 60%–75%, and its repellent effect on common mosquitoes such as Aedes aegypti and Culex pipiens pallens is more direct. Furthermore, the fabric's protective effect is stable. Utilizing a "microcapsule encapsulation + mosquito-repellent resin synergistic loading" technology, the mosquito-repellent rate remains ≥75% after 10 washes, addressing the pain point of existing fabrics where "mosquito-repellent components easily detach after spraying / padding processes." Conventional products experience a sharp drop in mosquito-repellent rate to below 50% or even become ineffective after 3–5 washes. The microcapsule wall material bonds tightly to the UHMWPE matrix interface, allowing for the slow release of mosquito-repellent components, providing effective protection for 3–6 months, far exceeding existing "instantaneous repellency" products (effective for 1–2 months).

[0053] The mosquito-repellent fabric substrate resin, its preparation method, and its application provided by this invention offer several advantages. Firstly, the components are safe: non-volatile, residue-free, and suitable for various scenarios. Specifically, the components do not detach: the mosquito-repellent ingredients are uniformly dispersed within the fiber through melt blending, rather than surface spraying / padding. There is no odor from the mosquito repellent during use, and no component migration or residue due to skin contact or friction, making it especially suitable for children and people with sensitive skin. Secondly, it is low-toxic and environmentally friendly: it uses low-toxicity mosquito-repellent ingredients such as picaridin and natural camphor leaf essential oil derivatives, complying with GB / T 30126-2013 "Testing and Evaluation of Mosquito Repellent Performance of Textiles" and EU REACH standards, avoiding the skin irritation and environmental pollution risks associated with the use of highly toxic DEET in existing products. Thirdly, the processing is safe: the entire process involves no solvent addition (melt spinning + physical mixing) and no VOC emissions, meeting green production requirements and differing from the environmental hazards of some existing products' "solvent-based padding finishing."

[0054] The present invention provides a mosquito-repellent fabric substrate resin, its preparation method, and its application, which balances durability, protection, and wearing comfort. Specifically, relying on the excellent mechanical properties of the UHMWPE substrate itself, the modified fiber breaking strength is ≥15cN / dtex, and the fabric breaking strength is ≥1000N / 5cm, far exceeding that of conventional cotton / chemical fiber mosquito-repellent fabrics (breaking strength is mostly 500-800N / 5cm). It can withstand outdoor friction and pulling (such as tent fabrics and outdoor clothing) and is not easily damaged. The fiber linear density (100-200dtex) and breaking elongation (15-25%) are optimized in the spinning stage. The weaving adopts breathable structures such as plain weave / plain needle, and the breathability of woven fabrics is ≥500mm / s, and that of knitted fabrics is ≥800mm / s. This solves the pain point of existing "functional fabrics being too stiff and not breathable", while the breathability of conventional mosquito-repellent fabrics is mostly 300-600mm / s.

[0055] The mosquito-repellent fabric substrate resin, its preparation method, and its applications provided by this invention offer several advantages: **Scenario Adaptability:** Flexible customization; **Form Customization:** Supports both machine-woven (outdoor tents, jackets) and knitted (underwear, gloves) fabrics, with adjustable warp and weft density, weight, and thickness (0.2-0.5mm) to suit all scenarios, from outdoor protection to home furnishings; **Function Stackable:** Post-processing stages can accommodate additional functions such as waterproofing, stain resistance, and antistatic properties (without affecting mosquito-repellent effect), distinguishing it from existing "single-function" mosquito-repellent fabrics and meeting the diverse needs of high-end users; **Adaptability to Extreme Environments:** The UHMWPE substrate itself is acid and alkali resistant and mildew resistant. Combined with mosquito-repellent functionality, it can be used in complex environments such as agricultural work clothes and field research equipment, whereas conventional mosquito-repellent fabrics are easily damaged and fail due to environmental corrosion.

[0056] In this specification, the invention has been described with reference to specific embodiments thereof. However, it will be apparent that various modifications and variations can be made without departing from the spirit and scope of the invention. Therefore, this specification should be considered illustrative rather than restrictive.

Claims

1. A resin for a mosquito-repellent fabric substrate, characterized in that, The substrate resin comprises the following components by weight percentage: UHMWPE resin 50%–70%; HDPE 20%~40%; Mosquito repellent microcapsules 2%–6%; Compatibilizer 0.5%–3%; Antioxidant 0.2%–2%; Spinning aids 1%–3%; The mosquito repellent resin contains 5% to 8% of camphor leaf essential oil derivatives.

2. The mosquito-repellent fabric substrate resin according to claim 1, characterized in that, The molecular weight of the UHMWPE resin is 1.5 million to 2 million.

3. The mosquito-repellent fabric substrate resin according to claim 1, characterized in that, The molecular weight of the HDPE is 300,000 to 500,000.

4. The mosquito-repellent fabric substrate resin according to claim 1, characterized in that, The mosquito-repellent microcapsules have a particle size of 5-20 μm, and the core material of the mosquito-repellent microcapsules is the active substance permethrin, which accounts for 20%-40% of the mass of the mosquito-repellent microcapsules. The camphor leaf essential oil derivative accounts for 3% to 8% of the mass of the mosquito repellent resin.

5. The mosquito-repellent fabric substrate resin according to claim 1, characterized in that, The compatibilizer is maleic anhydride-grafted PE with a grafting rate of ≥1.2%; the antioxidant is a 1010 / 168 composite agent; and the spinning aid is calcium stearate and polyethylene glycol.

6. A method for preparing a mosquito-repellent fabric substrate resin according to any one of claims 1 to 5, characterized in that, The preparation method includes the following steps: Premixing: UHMWPE resin and HDPE are added to a mixer for premixing; Additive mixing: Add compatibilizer, antioxidant, and spinning auxiliaries, heat to 70℃~90℃ and stir; Functional ingredient mixing: Add mosquito repellent microcapsules and mosquito-repellent resin, and stir; Melt blending: The mixture is fed into a twin-screw extruder with the following temperatures: feeding section 130℃~150℃, melting section 190℃~210℃, mixing section 200℃~220℃, homogenization section 180℃~200℃, die head 185℃~205℃, screw speed 350~450rpm, and feeding speed 20~30kg / h. The extrudate is water-cooled at 20-30℃, drawn, and pelletized to a particle size of 3-5mm, and then vacuum-dried at 70-90℃.

7. The method for preparing the mosquito-repellent fabric substrate resin according to claim 6, characterized in that, The stirring speed for adding mosquito-repellent microcapsules and mosquito-repellent resin is 300-400 rpm.

8. The application of the mosquito-repellent fabric substrate resin according to any one of claims 1 to 5 in mosquito-repellent fabrics.

9. The application according to claim 8, characterized in that, The mosquito-repellent fabric substrate resin is first spun by melt spinning and then woven.

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