Textile containing a complex insecticide and a method for preparing the same

Abstract

The present application relates to the technical field of textiles, and provides a textile containing a composite insecticide and a preparation method thereof. The present application applies an amide insecticide and a pyrethroid insecticide in the textile, so as to improve the insecticidal effect, solve the problem of poor biological effect of a single insecticide and the resistance problem of a traditional pyrethroid insecticide. Further, the present application uses a ternary compound of a water-based polyurethane, a silicone-modified acrylate resin and a crosslinking curing agent for a water-based film-forming resin as an adhesive, so that the three components synergistically realize the sustained and controllable release of the insecticide and the significant improvement of the water washing resistance. The results of the examples show that the textile prepared by the present application still has high biological activity after 20 times of WHO standard washing, and can effectively kill the mosquito and insect populations that have developed resistance to traditional insecticides.

Description

Technical Field

[0001] This invention relates to the field of textile technology, and in particular to a textile containing a compound insecticide and its preparation method. Background Technology

[0002] Malaria is a serious vector-borne infectious disease that severely threatens human health. In recent years, although improvements in mosquito control and prevention methods have brought malaria infection under control to some extent in some areas, the rapid reproduction and large population of mosquitoes have led to an increasing number of drug-resistant mosquitoes. Currently, pyrethroid insecticides are the main component of long-lasting mosquito nets, but relying solely on a single type of insecticide is insufficient to effectively control mosquito damage.

[0003] Cyprodinil (CAS Registry No.: 2375110-88-4) belongs to the m-diamid class of compounds and is an allosteric regulator of GABA (γ-aminobutyric acid) gated chloride ion channels in insects. The metabolite of cyprodinil, decyprodinil-cyprodinil, acts on the two subunits of the GABA receptor RDL1 and RDL2 in target pests, causing hyperexcitation, convulsions, and ultimately death in insects. It has both stomach poison and contact killing effects.

[0004] Existing technologies often integrate insecticides into polymer matrices to achieve their effect, but the sustained and controlled release of insecticides remains a technical challenge in this field. If the natural migration rate is too slow, it takes too long for the insecticide to reach an effective concentration, failing to provide immediate insecticidal effects; if the migration rate is too fast, the pesticide will be rapidly lost, making it difficult to maintain long-term protection. This is especially true in the textile industry, where fabrics inevitably undergo washing. During washing, the scouring effect of water and detergents easily damages the fragile bond between the insecticide and the fiber, leading to the leaching and loss of active ingredients. This not only wastes the pesticide but also causes the effective insecticidal concentration on the fabric surface to drop below the threshold in a short time, severely shortening the lifespan of protective products and failing to meet the requirements for sustained and controlled release.

[0005] One related technology discloses an insecticidal net material containing chlorfenapyr and pyrethroids; however, it does not disclose how to evenly distribute the insecticide within the material. Using only an impregnation method can easily lead to uneven pesticide distribution, affecting the insecticidal effect. Another related technology discloses an insecticidal composition containing amide compounds, the active ingredients of which include 4-methylphenyl-4-(trifluoromethyl)phenyl sulfone and amide compounds (such as tetrazolium acetamiprid). This approach mainly involves solid or liquid formulations for controlling specific pests, but does not mention how to control the release behavior of the two components in the matrix.

[0006] Currently, there are reports on using insecticides in combination with polymer adhesives to improve sustained-release properties, but usually a single adhesive is used, and the resulting film still has significant shortcomings in terms of wash resistance and sustained-release performance. One related technology provides a mosquito-repellent and washable fabric that improves wash resistance through a two-stage finishing process. The fabric is first finished with a mosquito-repellent finishing solution, and then a second finishing process is performed with a washable finishing solution containing a high concentration of adhesive, forming a composite structure of a "mosquito-repellent layer" and a "washable layer." However, this two-stage finishing process results in a lengthy production process, increased energy consumption and costs, and the two-bath finishing requires high precision in controlling process parameters, easily leading to problems such as uneven pesticide distribution. Furthermore, the concentration and release pathway of the insecticide differ between the inner and outer layers, making it difficult to truly achieve long-lasting and uniform release.

[0007] In conclusion, providing a textile that can release insecticides over a long period of time and effectively control mosquitoes is a technical problem that urgently needs to be solved. Summary of the Invention

[0008] In view of this, the present invention provides a textile containing a compound insecticide and a method for preparing the same. The textile provided by the present invention maintains a continuous and controllable release of the insecticide even after 20 washes, exhibiting good insecticidal effect, delaying the development of insecticide resistance in mosquitoes, and effectively killing mosquito populations that have developed resistance to traditional insecticides.

[0009] To achieve the above-mentioned objectives, the present invention provides the following technical solution: A textile containing a compound insecticide, characterized in that it comprises a textile substrate and a compound insecticide adhesive layer attached to the textile substrate; the compound insecticide adhesive layer comprises a compound insecticide, a ternary compound adhesive, and auxiliaries; the compound insecticide comprises amide insecticides and pyrethroid insecticides; and the content of amide insecticides in the textile containing the compound insecticide is 50-500 mg / m³. 2 The content of pyrethroid insecticides is 50~400 mg / m³. 2 .

[0010] Preferably, the amide insecticide includes one or more of the following: bromfenac, flufenacet, flonicamid, cyclobromfenac, cycloflufenac, tetrazolium, tetrachlorantraniliprole, bromfenac cyanamide, chlorantraniliprole, flubendiamide, isoxazolium, fluoxazolium, and thiocyclam. The pyrethroid insecticides include one or more of deltamethrin, permethrin, cis-cypermethrin, chlorpyrifos, tetrafluorobenzyl, and methoxyfenozide.

[0011] Preferably, the ternary compound adhesive comprises waterborne polyurethane, silicone-modified acrylate resin, and a crosslinking curing agent for waterborne film-forming resin; the dry weight of the crosslinking curing agent for waterborne film-forming resin is 0.5% to 8% of the total dry weight of the waterborne polyurethane and silicone-modified acrylate resin.

[0012] Preferably, the dry mass ratio of the waterborne polyurethane to the organosilicon-modified acrylate resin is 1:0.3~1, and the mass ratio of the composite insecticide to the dry mass of the ternary compound adhesive is 1:2.5~75. The crosslinking curing agent for the waterborne film-forming resin is selected from at least one of blocked isocyanate crosslinking agents, waterborne polycarbodiimide crosslinking agents, and waterborne multifunctional glycidyl ether type epoxy crosslinking agents.

[0013] Preferably, the additives include one or more of antioxidants, polycarboxylate polymeric dispersants, and fiber affinity film-forming aids.

[0014] The present invention also provides a method for preparing textiles containing compound insecticides as described above, comprising the following steps: A finishing solution is obtained by mixing amide insecticides, pyrethroid insecticides, ternary compound adhesives, additives and water. The textile is treated with the finishing solution and then dried to obtain the textile containing the compound insecticide.

[0015] Preferably, the pH value of the finishing solution is 6.0 to 8.0.

[0016] Preferably, the finishing solution comprises the following components by mass fraction: 0.1%~2% amide insecticide technical, 0.1%~2% pyrethroid insecticide technical, 1%~15% waterborne polyurethane, 0.3%~15% organosilicon-modified acrylate resin, 0.05%~2% crosslinking curing agent for waterborne film-forming resin, 1%~3% antioxidant, 0.8%~3% polycarboxylate polymeric dispersant, 0.3%~2% fiber affinity film-forming aid, 0.05%~1% pH adjuster, and the balance being water.

[0017] Preferably, the finishing method is padding or coating.

[0018] This invention provides a textile containing a compound insecticide, comprising a textile substrate and a compound insecticide adhesive layer attached to the textile substrate; the compound insecticide adhesive layer comprises a compound insecticide, a ternary compound adhesive, and auxiliaries; the compound insecticide comprises amide insecticides and pyrethroid insecticides; in the textile containing the compound insecticide, the content of amide insecticides is 50~500 mg / m³. 2 The content of pyrethroid insecticides is 50~400 mg / m³.2 This invention combines amide insecticides and pyrethroid insecticides in textiles, and strictly controls the content of the two insecticides in the textiles. This improves the insecticidal effect and solves the problems of poor biological efficacy of single insecticides and resistance to traditional pyrethroid insecticides.

[0019] Furthermore, this invention employs a ternary compound of waterborne polyurethane, silicone-modified acrylate resin, and waterborne film-forming resin with a crosslinking curing agent as an adhesive. The synergistic effect of these three components achieves sustained and controllable release of the insecticide and significantly improves its washability. The waterborne polyurethane molecular chain contains numerous urethane and urea bonds, which can tightly bond with the surfaces of various textile fibers such as cotton and polyester through hydrogen bonds and van der Waals forces, providing strong adhesion to textile substrates for the adhesive film. After the silicone-modified acrylate resin film is formed, the polydimethylsiloxane (PDMS) segments on the molecular chain, due to their low surface energy, spontaneously migrate and accumulate to the film surface, forming a low-surface-energy hydrophobic layer. This hydrophobic layer significantly reduces the water absorption and swelling of the resin film during washing, reducing the penetration of external moisture into the film interior, thereby effectively inhibiting the loss of insecticide from the film with water molecules.

[0020] Furthermore, the crosslinking curing agent used in this invention for the waterborne film-forming resin is selected from at least one of blocked isocyanate crosslinking agents, waterborne polycarbodiimide crosslinking agents, and waterborne multifunctional glycidyl ether type epoxy crosslinking agents. The blocked isocyanate crosslinking agent, at room temperature, has its isocyanate groups protected by the blocking agent, allowing it to stably coexist with the waterborne polyurethane and silicone-modified acrylate resin in the finishing solution. During the drying process, as the temperature rises above the deblocking temperature, the released isocyanate groups undergo a crosslinking reaction with the active hydroxyl groups on the waterborne polyurethane molecular chain, forming chemical crosslinking points. These chemical crosslinking points, together with the interpenetrating network structure formed by the physical blending of the waterborne polyurethane and silicone-modified acrylate resin, constitute a "physical-chemical dual crosslinking" system.

[0021] Waterborne polycarbodiimide crosslinking agents contain carbodiimide groups (-N=C=N-), which react with carboxyl groups (-COOH) on the resin molecular chain to form stable N-acylurea crosslinking bonds. These crosslinking agents have advantages such as low toxicity, high efficiency, no volatile organic gases, and non-yellowing of the film formed. They also have a long mixing life and can undergo crosslinking reactions at room temperature.

[0022] Waterborne multifunctional glycidyl ether-type epoxy crosslinking agents contain multiple epoxy groups, which undergo ring-opening addition reactions with carboxyl (-COOH), amino (-NH2), or hydroxyl (-OH) groups on the resin molecular chain to form a stable ether crosslinking network. These crosslinking agents have high water solubility, low chlorine content, and are fiber-friendly, significantly improving the water resistance and adhesion of coatings.

[0023] The present invention also controls the amount of crosslinking curing agent to be 0.5% to 8% of the total dry weight of waterborne polyurethane and silicone-modified acrylate resin. When the amount of crosslinking curing agent is less than 0.5% of the total dry weight of waterborne polyurethane and silicone-modified acrylate resin, the crosslinking density is insufficient, and an effective chemical crosslinking network cannot be formed, resulting in limited improvement in water resistance and slow-release effect. When the amount is higher than 8%, the excessively high crosslinking density leads to an overly rigid film layer, resulting in a stiff fabric feel and reduced air permeability. At the same time, too many crosslinking points may excessively close the pores inside the film, preventing insecticide molecules from being effectively released to the fabric surface and affecting the insecticidal effect.

[0024] The results of the examples show that the textiles prepared by the present invention still have high biological activity after 20 washes according to WHO standards (Guidelines for laboratory and field-testing of long-lasting insecticidal nets). After 3 minutes of contact with the test textiles washed 20 times, the 60-minute knockdown rate and 24-hour mortality rate of sensitive mosquitoes can reach 100%, and the 60-minute knockdown rate of resistant mosquitoes can reach more than 75%, and the 24-hour mortality rate can reach more than 70%. Detailed Implementation

[0025] This invention provides a textile containing a compound insecticide, comprising a textile substrate and a compound insecticide adhesive layer attached to the textile substrate; the compound insecticide adhesive layer comprises a compound insecticide, a ternary compound adhesive, and auxiliaries; the compound insecticide comprises amide insecticides and pyrethroid insecticides; In the textiles containing compound insecticides, the content of amide insecticides is 50~500 mg / m². 2 The content of pyrethroid insecticides is 50~400 mg / m³. 2 .

[0026] The textile containing a compound insecticide provided by this invention includes a textile substrate. In this invention, the textile substrate is preferably one or more of woven textiles, knitted textiles, and nonwoven fabrics; this invention does not have special requirements for the material of the textile substrate, and any material well known to those skilled in the art can be used; in a specific embodiment of this invention, the textile substrate can be a polyester mesh. This invention does not have special requirements for the type of textile, and it can specifically be a mosquito net.

[0027] The textile containing a compound insecticide provided by the present invention includes a compound insecticide adhesive layer attached to the textile substrate. In the present invention, the components of the compound insecticide adhesive layer include a compound insecticide, a ternary compound adhesive, and auxiliaries; the compound insecticide includes amide insecticides and pyrethroid insecticides; the amide insecticides preferably include one or more of the following: bromfenoxam, flufenoxam, flubendiamide, isoxazolamide, fluoxazolamide, flonicamid, cyclobrombutamide, cyproconazole, tetrazolium, tetrachlorantraniliprole, chlorantraniliprole, and thiocyclobenzamide; the pyrethroid insecticides preferably include one or more of the following: deltamethrin, permethrin, cis-cypermethrin, chlorfluazuron, tetraflubenzuron, and methoxyfenozide; in a specific embodiment of the present invention, the compound insecticide is preferably cyproconazole and deltamethrin. In the textile containing the compound insecticide, the content of amide insecticide is preferably 50-500 mg / m³. 2 Specifically, the concentrations can be 50, 80, 90, 100, 110, 150, 200, 300, 400, or 500 mg / m². 2 The preferred content of pyrethroid insecticides is 50~400 mg / m³. 2 Specifically, the dosage can be 50, 100, 150, 165, 170, 200, 300, or 400 mg / m². 2 This invention combines amide insecticides and pyrethroid insecticides, which can improve the insecticidal effect and solve the problems of poor biological efficacy of single insecticides and resistance to traditional pyrethroid insecticides.

[0028] In this invention, the ternary compound adhesive comprises waterborne polyurethane, silicone-modified acrylate resin, and a crosslinking curing agent for waterborne film-forming resin; the mass fraction of polydimethylsiloxane segments in the silicone-modified acrylate resin is preferably 5% to 15%, specifically 5%, 8%, 10%, 12%, or 15%; the dry mass ratio of the waterborne polyurethane to the silicone-modified acrylate resin is preferably 1:0.3 to 1, specifically 1:0.3, 1:0.5, 1:0.6, 1:0.7, 1:0.8, or 1:1; this invention preferably controls the ratio of waterborne polyurethane to silicone-modified acrylate resin within the above range, which can form a continuous and complete hydrophobic layer on the membrane surface, reduce the water absorption rate of the membrane, improve the washability and slow-release effect, and at the same time ensure the adhesion of the membrane to textile fibers, avoid increasing membrane brittleness, and avoid the phenomenon of micro-cracks in the film and accelerated pesticide loss during washing.

[0029] In this invention, the dry weight of the crosslinking curing agent for the waterborne film-forming resin is preferably 0.5% to 8% of the total dry weight of the waterborne polyurethane and silicone-modified acrylate resins, specifically 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, or 8%. The crosslinking curing agent for the waterborne film-forming resin is preferably selected from at least one of blocked isocyanate crosslinking agents, waterborne polycarbodiimide crosslinking agents, and waterborne multifunctional glycidyl ether epoxy crosslinking agents; the deblocking temperature of the blocked isocyanate crosslinking agent is preferably 110°C to 160°C.

[0030] In this invention, the ratio of the mass of the composite insecticide to the dry mass of the ternary compound adhesive is preferably 1:2.5 to 75, specifically 1:2.5, 1:7, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60 or 1:75.

[0031] In this invention, the additives preferably include one or more of antioxidants, polycarboxylate polymeric dispersants, and fiber affinity film-forming aids; the antioxidants preferably include one or more of butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate, tea polyphenols, phytic acid, and tert-butylhydroquinone; the polycarboxylate polymeric dispersants preferably include one or more of sodium polyacrylate, sodium maleic acid-acrylic acid copolymer, and polycarboxylate dispersants; the fiber affinity film-forming aids preferably include one or more of sodium carboxymethyl chitosan and chitosan quaternary ammonium salt; and the pH adjusters preferably include one or more of citric acid, triethanolamine, and sodium dihydrogen phosphate. In specific embodiments of the present invention, the additives preferably include antioxidants, polycarboxylate polymeric dispersants, and fiber affinity film-forming aids simultaneously; the mass ratio of the antioxidant to the ternary compound adhesive is preferably 1~3:2~25; the mass ratio of the polycarboxylate polymeric dispersant to the ternary compound adhesive is preferably 0.8~3:2~25; and the mass ratio of the fiber affinity film-forming aid to the ternary compound adhesive is preferably 0.3~2:2~25. The present invention, by adding antioxidants, can inhibit and delay the degradation and aging of textile materials due to oxidation reactions, thereby extending their service life; by adding polycarboxylate polymeric dispersants, it stabilizes insecticide particles from within the system, preventing agglomeration and sedimentation during storage, while reducing the migration of small molecules and lowering the dissolution rate of active ingredients during washing; by adding fiber affinity film-forming aids, it strengthens the adhesion between the pesticide film and the fabric fibers from the outside, preventing the entire film from peeling off, while also adjusting the rheological properties of the system and improving the workability.

[0032] The present invention also provides a method for preparing textiles containing compound insecticides as described above, comprising the following steps: A finishing solution is obtained by mixing amide insecticides, pyrethroid insecticides, ternary compound adhesives, additives and water. The textile is treated with the finishing solution and then dried to obtain the textile containing the compound insecticide.

[0033] This invention involves mixing an amide insecticide, a pyrethroid insecticide, a ternary compound adhesive, an adjuvant, and water to obtain a finishing solution. In this invention, the pH value of the finishing solution is 6-8, specifically 7.

[0034] In this invention, the finishing liquid preferably comprises the following components by mass fraction: 0.1%~2% of amide insecticide technical grade, specifically 0.2%, 0.3%, 0.5%, 1% or 1.5%; 0.1%~2% of pyrethroid insecticide technical grade, specifically 0.2%, 0.5%, 0.8%, 1% or 1.5%; 1%~15% of waterborne polyurethane, specifically 5%, 6%, 10% or 12%; and 0.3%~15% of organosilicon-modified acrylate resin, specifically 2.5%, 3%, 5%, 10% or 1%. 2%, waterborne film-forming resin crosslinking curing agent 0.05%~2%, specifically 0.3%, 0.4%, 1% or 1.5%, antioxidant 1%~3%, specifically 1% or 2%, polycarboxylate polymeric dispersant 0.8%~3%, specifically 1% or 1.5%, fiber affinity film-forming aid 0.3%~2%, specifically 0.8% or 0.9%, pH adjuster 0.05%~1%, balance being water; the amide-based insecticide technical and the pyrethroid-based insecticide technical need to be ground into powder, with a suitable particle size range of D. 90 ≤20μm, this particle size can ensure the uniform dispersion of the active ingredient in the system and avoid agglomeration; in a specific embodiment of the present invention, it is preferable to first mix the amide insecticide active ingredient, pyrethroid active ingredient, ternary compound adhesive, antioxidant, polycarboxylate polymeric dispersant and water evenly, and then add the fiber affinity film-forming aid and mix evenly to obtain the finishing solution.

[0035] After obtaining the finishing solution, the present invention uses the finishing solution to finish the textile and then dries it to obtain the textile containing the compound insecticide. In the present invention, the finishing method is preferably padding or coating; in a specific embodiment of the present invention, it is preferable to first pad the textile substrate to make it evenly spread, then fully impregnate it with the finishing solution, and then pass the fully impregnated textile through rollers to make the finishing solution evenly adhere to the textile substrate.

[0036] In this invention, the drying temperature is preferably 90~160℃, and the drying time is preferably 30~120s. In this invention, when the crosslinking agent used is a blocked isocyanate crosslinking agent, during the drying process, as the temperature rises above the deblocking temperature, the released isocyanate groups will undergo a crosslinking reaction with the active hydroxyl groups on the waterborne polyurethane molecular chain, forming chemical crosslinking points.

[0037] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0038] The waterborne polyurethane used in the following examples is WANNATE® WPU-100, with a solid content of 40%, manufactured by Wanhua Chemical Group Co., Ltd.; the silicone-modified acrylate resin is QM 3005, with a solid content of 50%, manufactured by Huizhou Qiangmao Chemical Technology Co., Ltd.; the blocked isocyanate crosslinking agent is HD-8035, with a solid content of 35%, manufactured by Changzhou Houding Chemical Co., Ltd.; and the waterborne polycarbodiimide crosslinking agent is Nisshinbo CARBODILITE V-02, with a solid content of 40%, manufactured by Shenzhen Xiangrun New Materials Co., Ltd.

[0039] Polycarboxylate polymeric dispersants: Sodium polyacrylate (PAA) is manufactured by Shandong Taihe Technology Co., Ltd.; Sodium maleic acid-acrylic acid copolymer is manufactured by BASF Germany, with the brand name SokalanCP-5.

[0040] Fiber affinity film-forming aids: N,O-carboxymethyl chitosan sodium, manufactured by Zhejiang Jinke Pharmaceutical Co., Ltd.; chitosan quaternary ammonium salt, manufactured by Nantong Lvshen Bioengineering Co., Ltd.

[0041] Example 1 By mass fraction, 0.3% of cyprodinil technical, 0.5% of deltamethrin technical, 5% of waterborne polyurethane, 3% of silicone-modified acrylate resin, 0.3% of blocked isocyanate crosslinking agent, 2% of butylated hydroxytoluene, 0.2% of sodium dihydrogen phosphate, 1% of sodium polyacrylate, and 86.8% of water are mixed evenly, and then 0.9% of N,O-carboxymethyl chitosan sodium is added and mixed evenly to obtain a finishing solution with a pH of 7 at room temperature. The finishing solution is applied to a fabric (polyester web) by padding. The fabric fully impregnated with the finishing solution is passed through rollers to ensure even adhesion of the finishing solution, and finally dried in a dryer at 120℃ for 45 seconds to obtain a polyester web containing cyprodinil and deltamethrin.

[0042] Example 2 By mass fraction, 0.5% brofenoxam technical, 0.8% cis-cypermethrin technical, 6% waterborne polyurethane, 2.5% silicone-modified acrylate resin, 0.4% waterborne polycarbodiimide crosslinking agent, 1% butylated hydroxyanisole, 0.1% citric acid, 1.5% sodium maleic acid-acrylate copolymer, and 86.4% water were mixed evenly, and then 0.8% chitosan quaternary ammonium salt was added and mixed evenly to obtain a finishing solution with a pH of 6.5 at room temperature. The finishing solution was applied to a fabric (polyester web) by padding. The fabric, fully impregnated with the finishing solution, was passed through rollers to ensure even adhesion of the finishing solution. Finally, it was dried in a dryer at 110℃ for 60 seconds to obtain a polyester web containing brofenoxam and cis-cypermethrin.

[0043] Comparative Example 1 By mass fraction, 0.5% deltamethrin technical, 5% waterborne polyurethane, 3% silicone-modified acrylate resin, 0.3% blocked isocyanate crosslinking agent, 2% butylated hydroxytoluene, 0.2% sodium dihydrogen phosphate, 1% sodium polyacrylate, and 87.1% water are mixed evenly, and then 0.9% N,O-carboxymethyl chitosan sodium is added and mixed evenly to obtain a finishing solution with a pH of 6.7 at room temperature. The finishing solution is applied to the fabric (polyester web) by padding. First, the polyester web is prepared by padding equipment to make it evenly spread. Then, the polyester web is fully immersed in the finishing solution in a liquid tank. The fully immersed fabric is then passed through rollers to make the finishing solution evenly adhere to the fabric. Finally, it is dried in a dryer at 120℃ for 45 seconds to obtain a polyester web containing deltamethrin.

[0044] Comparative Example 2 The only difference between this finishing solution formulation and that of Example 1 is that silicone-modified acrylate resin is not added, and the water content is changed to 89.8%. The manufacturing process remains the same.

[0045] Comparative Example 3 The only difference between this finishing solution formulation and that of Example 1 is that waterborne polyurethane is not added, and the water content is changed to 91.8%. The manufacturing process is the same.

[0046] Comparative Example 4 The only difference between this finishing solution formulation and that of Example 1 is that a blocked isocyanate crosslinking agent is not added, and the water content is changed to 87.1%. The manufacturing process remains the same.

[0047] Comparative Example 5 By mass fraction, 0.12% of cyprodinil technical, 0.68% of deltamethrin technical, 5% of waterborne polyurethane, 3% of silicone-modified acrylate resin, 0.3% of blocked isocyanate crosslinking agent, 2% of butylated hydroxytoluene, 0.2% of sodium dihydrogen phosphate, 1% of sodium polyacrylate, and 86.8% of water were mixed evenly, and then 0.9% of N,O-carboxymethyl chitosan sodium was added and mixed evenly to obtain a finishing solution. The pH of the finishing solution was 7 at room temperature. The preparation process was the same as in Example 1.

[0048] Comparative Example 6 By mass fraction, 0.65% of cyprodinil technical, 0.15% of deltamethrin technical, 5% of waterborne polyurethane, 3% of silicone-modified acrylate resin, 0.3% of blocked isocyanate crosslinking agent, 2% of butylated hydroxytoluene, 0.2% of sodium dihydrogen phosphate, 1% of sodium polyacrylate, and 86.8% of water were mixed evenly, and then 0.9% of N,O-carboxymethyl chitosan sodium was added and mixed evenly to obtain a finishing solution. The pH value of the finishing solution was 7.0 at room temperature. The preparation process was the same as in Example 1.

[0049] Comparative Example 7 By mass fraction, 0.3% of oxadiazon technical, 0.5% of deltamethrin technical, 5% of waterborne polyurethane, 3% of silicone-modified acrylate resin, 0.3% of blocked isocyanate crosslinking agent, 2% of butylated hydroxytoluene, 0.2% of sodium dihydrogen phosphate, 1% of sodium polyacrylate, and 86.8% of water were mixed evenly, and then 0.9% of N,O-carboxymethyl chitosan sodium was added and mixed evenly to obtain a finishing solution. The pH of the finishing solution was 7 at room temperature. The preparation process was the same as in Example 1.

[0050] Test Example 1 The polyester nets containing cyprodinil and deltamethrin prepared in Example 1 were washed 20 times according to WHO standards (Guidelines for laboratory and field-testing of long-lasting insecticidal nets), and bioassays were performed. Under a standard WHO cone, 200 insecticide-free female mosquitoes (2-5 days old) and pyrethroid-resistant female mosquitoes were exposed to the polyester nets, 5 mosquitoes per cone, for 3 minutes. Mosquito knockdown was recorded after 60 minutes, and mosquito mortality was recorded after 24 hours. A polyester net without any insecticide loading was used as a blank control. The test environment was 27±2℃ and relative humidity 75±10%. The test results are shown in Table 1.

[0051] Meanwhile, the polyester net containing deltamethrin prepared in Comparative Example 1 was subjected to bioassay analysis for insecticide-free resistant female mosquitoes and pyrethroid insecticide-resistant female mosquitoes using the same method. The test results are shown in Table 2.

[0052] Table 1. Bioassay Analysis of Polyester Web Containing Cyprodinium and Delcypermethrin (Example 1)

[0053] Table 2 Bioassay Analysis of Polyester Mesh Containing Delemyl Cypermethrin (Comparative Example 1)

[0054] As shown in Tables 1 and 2, the polyester nets containing cyprodinil and deltamethrin exhibited a 100% knockdown rate and 24-hour mortality rate against non-resistant mosquitoes both before and after 20 washes. Before washing, the polyester nets containing cyprodinil and deltamethrin showed a 100% knockdown rate and a 92% mortality rate against resistant mosquitoes within 60 minutes. After 20 washes, the knockdown rate remained at 88% within 60 minutes and the mortality rate at 24 hours. In contrast, the polyester net containing deltamethrin prepared in Comparative Example 1 showed a 99% mortality rate against non-resistant mosquitoes within 24 hours before washing, and a 90% mortality rate after 20 washes. Before washing, the knockdown rate against resistant mosquitoes within 60 minutes was only 45%, and the mortality rate within 24 hours was only 28%. After 20 washes, the knockdown rate within 60 minutes decreased to 16%, and the mortality rate within 24 hours decreased to 12%. The above results show that the present invention, by combining amide insecticides and pyrethroid insecticides, can effectively improve the insecticidal effect, solve the problem of poor biological efficacy of single insecticides and the resistance problem of traditional pyrethroid insecticides.

[0055] During the 20 washing cycles of the polyester web containing cyprodinil and deltamethrin prepared in Example 1, the content of cyprodinil and deltamethrin in the fabric was tested, and the test results are shown in Table 3.

[0056] Table 3. Test Table of Insecticide Content in Polyester Nets Containing Cyprodinium and Deltamethrin

[0057] As can be seen from the data in Table 3, after 20 washes, the polyester web still contains a relatively large amount of cyprodinil and deltamethrin, indicating that the insecticide has strong adhesion to the fabric, good wash resistance, and can achieve continuous and controllable release of the insecticide.

[0058] Test Example 2 Polyester nets containing cyprodinil and deltamethrin, prepared in Comparative Examples 2, 3, and 4, were washed 20 times according to WHO standards (Guidelines for laboratory and field-testing of long-lasting insecticidal nets) and subjected to bioassays. Under a standard WHO cone, 200 2-5 day old female mosquitoes without insecticide resistance and pyrethroid-resistant female mosquitoes were exposed to the polyester nets, 5 mosquitoes per cone, for 3 minutes. Mosquito knockdown was recorded after 60 minutes, and mosquito mortality was recorded after 24 hours. A polyester net without any insecticide loading was used as a blank control. The test environment was 27±2℃ and relative humidity 75±10%. The test results are shown in Table 4.

[0059] Table 4 Bioassay analysis of polyester nets prepared in Comparative Examples 2, 3 and 4 (no insecticide resistance)

[0060] Table 5 Bioassay analysis of polyester nets prepared in Comparative Examples 2, 3 and 4 (with insecticide resistance)

[0061] During the 20 washing cycles of the polyester webs prepared in Comparative Examples 2, 3, and 4, the contents of cyprodinil and deltamethrin in the fabrics were tested, and the test results are shown in Tables 6, 7, and 8.

[0062] Table 6. Test table of pesticide content in polyester nets prepared in Comparative Example 2

[0063] Table 7. Test table of pesticide content in polyester nets prepared in Comparative Example 3

[0064] Table 8. Test table of pesticide content in polyester nets prepared in Comparative Example 4

[0065] As can be seen from the data in Tables 4-8, Comparative Example 2 (lacking silicone-modified acrylate): Although it has a chemically cross-linked membrane constructed from waterborne polyurethane and a cross-linking agent, it lacks a hydrophobic surface layer of siloxane segments. During washing, the membrane absorbs water and swells more intensely, accelerating the insecticide dissolution rate. After 20 washes, the total pesticide residue rate was approximately 51%, significantly lower than the 61% in Example 1; the 24-hour mortality rate of resistant mosquitoes decreased from 80% in Example 1 to 54%, verifying the crucial role of the silicone component in improving wash resistance and maintaining long-term insecticide resistance.

[0066] Comparative Example 3 (lacking waterborne polyurethane): Relying solely on silicone-modified acrylate for film formation, the hydrogen bonding force with the fiber was significantly weakened, resulting in insufficient film adhesion. During washing, the film was prone to damage and detachment, leading to the fastest pesticide loss. After 20 washes, the total pesticide residue rate was only 23%, and the mortality rate of resistant mosquitoes decreased to 13%, similar to the effect of Comparative Example 1 using deltamethrin alone. This indicates that waterborne polyurethane is the fundamental core component ensuring the integrity and adhesion of the film structure.

[0067] Comparative Example 4 (lacking crosslinking agent): The two resins were only physically blended and interpenetrated, without a chemical crosslinking network. The free volume within the membrane was large, the diffusion channels for pesticide molecules were wide, and the leaching rate was higher than that of the fully crosslinked system. After 20 washes, the total pesticide residue rate was approximately 32%, with the effect falling between Comparative Example 3 and Comparative Example 2. This verifies the necessity of crosslinking agents for dense membrane structures and achieving controlled sustained release.

[0068] Test Example 3 The polyester nets containing cyprodinil and deltamethrin prepared in Comparative Examples 5 and 6 were washed 20 times according to WHO standards (Guidelines for laboratory and field-testing of long-lasting insecticidal nets) and subjected to bioassay analysis. Under a standard WHO cone, 200 2-5 day old female mosquitoes without insecticide resistance and pyrethroid-resistant female mosquitoes were exposed to the polyester nets, 5 mosquitoes per cone, for 3 minutes. Mosquito knockdown was recorded after 60 minutes, and mosquito mortality was recorded after 24 hours. A polyester net without any insecticide loading was used as a blank control. The test environment was 27±2℃ and relative humidity 75±10%. The test results are shown in Tables 9 and 10.

[0069] Table 9. Bioassay Analysis of Polyester Web Prepared in Comparative Example 5

[0070] Table 10 Bioassay analysis of the polyester mesh prepared in Comparative Example 6

[0071] During the 20 washing cycles of the polyester webs prepared in Comparative Examples 5 and 6, the contents of cyprodinil and deltamethrin in the fabric were tested, and the test results are shown in Tables 11 and 12.

[0072] Table 11 Test table of pesticide content in polyester nets prepared in Comparative Example 5

[0073] Table 12 Test table of pesticide content in polyester nets prepared in Comparative Example 6

[0074] Comparative Example 5 (Cyprodinium less than 50 mg / m³) 2 The total insecticide load was similar to that in Example 1, but the proportion of amide insecticides was too low, resulting in a significant reduction in effectiveness against resistant mosquitoes. Although the knockdown and mortality rates against sensitive mosquitoes remained at 100%, the effectiveness against resistant mosquitoes was significantly reduced after 20 washes, with the knockdown rate dropping to as low as 15% and the mortality rate dropping to as low as 10%.

[0075] Comparative Example 6 (deltamethrin below 50 mg / m³) 2 The insufficient proportion of pyrethroids led to a significant decrease in the rapid knockdown effect, with the 60-minute knockdown rate being significantly lower than that in Example 1. At the same time, the compound ratio deviated from the optimal range. Even with an increase in the amount of cyprofen added, the mortality rate of resistant mosquitoes did not increase significantly, indicating that its synergistic effect with pyrethroids was reduced.

[0076] The above results verify that controlling amide insecticides at 50~500 mg / m³ is effective. 2 Pyrethroid insecticides should be controlled at 50-400 mg / m³. 2 Within this range, it is a necessary condition to ensure the synergistic effect of compound formulations, balance knockdown speed and mortality rate, and effectively combat resistant mosquitoes.

[0077] Test Example 4 The polyester nets containing oxadiazon and deltamethrin prepared in Comparative Example 7 were washed 20 times according to WHO standards (Guidelines for laboratory and field-testing of long-lasting insecticidal nets) and subjected to bioassay analysis. Under a standard WHO cone, 200 2-5 day old female mosquitoes without insecticide resistance and pyrethroid-resistant female mosquitoes were exposed to the polyester nets, 5 mosquitoes per cone, for 3 minutes. Mosquito knockdown was recorded after 60 minutes, and mosquito mortality was recorded after 24 hours. A polyester net without any insecticide loading was used as a blank control. The test environment was 27±2℃ and relative humidity 75±10%. The test results are shown in Table 13.

[0078] Table 13 Bioassay Analysis of Polyester Web Prepared in Comparative Example 7

[0079] Comparative Example 7: When the insecticide cyprodinil was replaced with oxadiazon, although its knockdown rate and mortality rate against non-resistant mosquitoes were 100%, its knockdown rate and mortality rate against resistant mosquitoes were significantly lower than those of the pyrethroid-cyprodinil combination sample.

[0080] Test Example 5 The polyester nets containing brofentanil and cis-cypermethrin prepared in Example 2 were subjected to 20 washes according to WHO standards (Guidelines for laboratory and field-testing of long-lasting insecticidal nets), and bioassays were performed. Under a standard WHO cone, 200 insecticide-free female mosquitoes (2-5 days old) and pyrethroid-resistant female mosquitoes were exposed to the polyester nets, 5 mosquitoes per cone, for 3 minutes. Mosquito knockdown was recorded after 60 minutes, and mosquito mortality was recorded after 24 hours. A polyester net without any insecticide loading was used as a blank control. The test environment was 27±2℃ and relative humidity 75±10%. The test results are shown in Table 14.

[0081] Table 14 Bioassay Analysis of Polyester Web Prepared in Example 2

[0082] Example 2: Replacing the insecticides cyprodinil and deltamethrin with bromfenac and cis-cypermethrin resulted in a 100% knockdown and mortality rate against non-resistant mosquitoes, as well as a high knockdown and mortality rate against resistant mosquitoes.

[0083] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A textile containing a compound insecticide, characterized in that, The invention includes a textile substrate and a composite insecticide adhesive layer attached to the textile substrate; the composite insecticide adhesive layer comprises a composite insecticide, a ternary compound adhesive, and additives; the composite insecticide includes amide insecticides and pyrethroid insecticides. In the textiles containing compound insecticides, the content of amide insecticides is 50~500 mg / m². 2 The content of pyrethroid insecticides is 50~400 mg / m³. 2 .

2. The textile containing a compound insecticide according to claim 1, characterized in that, The amide insecticides include one or more of the following: bromfenac-methyl, flufenoxuron-methyl, flupyradifuron-methyl, cyclobromhizobium, cyclopropionate, tetrazolium-methyl, tetrachlorantraniliprole, brofenoxuron-methyl, chlorantraniliprole, flubendiamide, isoxazolium-methyl, fluoxazolium-methyl, and thiocyclam. The pyrethroid insecticides include one or more of deltamethrin, permethrin, cis-cypermethrin, chlorpyrifos, tetrafluorobenzyl, and methoxyfenozide.

3. The textile containing a compound insecticide according to claim 1, characterized in that, The ternary compound adhesive comprises waterborne polyurethane, silicone-modified acrylate resin, and a crosslinking curing agent for waterborne film-forming resin; the dry weight of the crosslinking curing agent for waterborne film-forming resin is 0.5% to 8% of the total dry weight of the waterborne polyurethane and silicone-modified acrylate resin.

4. The textile containing a compound insecticide according to claim 3, characterized in that, The dry mass ratio of the waterborne polyurethane to the organosilicon-modified acrylate resin is 1:0.3~1, and the mass ratio of the composite insecticide to the dry mass of the ternary compound adhesive is 1:2.5~75. The crosslinking curing agent for the waterborne film-forming resin is selected from at least one of blocked isocyanate crosslinking agents, waterborne polycarbodiimide crosslinking agents, and waterborne multifunctional glycidyl ether type epoxy crosslinking agents.

5. The textile containing a compound insecticide according to claim 1, characterized in that, The additives include one or more of antioxidants, polycarboxylate polymeric dispersants, and fiber affinity film-forming aids.

6. The textile containing a compound insecticide according to claim 1, characterized in that, The textile substrate includes one or more of woven textiles, knitted textiles, and nonwoven fabrics.

7. The method for preparing the textile containing the compound insecticide according to any one of claims 1 to 6, characterized in that, Includes the following steps: A finishing solution is obtained by mixing amide insecticides, pyrethroid insecticides, ternary compound adhesives, additives and water. The textile is treated with the finishing solution and then dried to obtain the textile containing the compound insecticide.

8. The preparation method according to claim 7, characterized in that, The pH value of the finishing solution is 6.0~8.

0.

9. The preparation method according to claim 7, characterized in that, The finishing solution comprises the following components by mass fraction: 0.1%~2% amide insecticide technical, 0.1%~2% pyrethroid insecticide technical, 1%~15% waterborne polyurethane, 0.3%~15% organosilicon-modified acrylate resin, 0.05%~2% crosslinking curing agent for waterborne film-forming resin, 1%~3% antioxidant, 0.8%~3% polycarboxylate polymeric dispersant, 0.3%~2% fiber affinity film-forming aid, 0.05%~1% pH adjuster, and the balance being water.

10. The preparation method according to claim 7, characterized in that, The finishing method is padding or coating.

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