A micro-nano mineral hydroxyl negative ion household wardrobe mothproofing and mothproofing patch and a preparation method thereof

Abstract

The present application relates to the technical field of household insect prevention and deodorization functional materials, in particular to a micro-nano mineral hydroxyl anion household wardrobe insect prevention and moth prevention paste and a preparation method thereof, which comprises, from outside to inside, a breathable slow-release surface layer, a micro-nano mineral functional core layer, a moisture-proof water-locking bottom layer and a back adhesive release layer, forming a four-layer integrated structure. The present application: the modified mineral powder is mixed with fibers, moisturizing aids, dispersion stabilizers and pore adjusters to form a uniform slurry; the slurry is formed by papermaking and dried in stages at low temperature to obtain a mineral functional core layer with controlled water content; then the breathable slow-release surface layer, the mineral functional core layer and the moisture-proof water-locking bottom layer are hot-pressed, and pressure-sensitive adhesive is roller-coated on the back of the bottom layer and a release film is attached; finally, the product is cut into single pieces and vacuum-sealed independently.

Description

Technical Field

[0001] This invention relates to the field of functional materials for home insect prevention and deodorization, specifically a micro-nano mineral hydroxyl negative ion home wardrobe insect and moth prevention patch and its preparation method. Background Technology

[0002] Clothes stored in a closed wardrobe for extended periods are highly susceptible to infestation by pests such as silverfish, clothes moths, booklice, and mites in high-humidity environments, while also developing mold and unpleasant odors. Currently, the following types of products are primarily used for insect and moth prevention in household wardrobes.

[0003] The first category is mothballs and synthetic insect repellent tablets. These products contain naphthalene, paradichlorobenzene, and pyrethroid insect repellents, which rely on volatile substances to repel and kill insects. These volatile substances easily adhere to clothing, and contact with skin may cause allergic reactions. Children, pregnant women, and people with respiratory sensitivities are generally not suitable for use; furthermore, their effectiveness diminishes rapidly with evaporation, requiring frequent replacement.

[0004] The second category consists of insect repellent sachets made with natural fragrances such as lavender and camphor wood chips. These products rely solely on scent to repel pests and cannot damage insect eggs or cell membranes. They also have weak moisture-proof and antibacterial properties. In humid environments, the fragrances themselves are prone to absorbing moisture and becoming ineffective, and may even mold.

[0005] The third category is negative ion non-woven fabric insect repellent patches. These products use mineral powder as a functional component, but they have two prominent problems. Firstly, the mineral powder particles are generally larger than micrometers, resulting in a small surface area and insufficient contact with air, leading to insufficient release of hydroxyl negative ions. The powder is not surface-modified, making it prone to agglomeration and uneven dispersion within the carrier, resulting in poor breathability and a short release cycle. Secondly, these products are mostly single-layered drug-loaded structures, with the mineral powder directly exposed or only wrapped in a single layer of non-woven fabric, lacking a moisture-proof and moisture-locking interlayer. Condensed moisture in the wardrobe can easily penetrate the functional layer, causing the mineral powder to clump and become ineffective. Simultaneously, the release rate is uncontrollable; the initial high release concentration may irritate the respiratory tract, followed by rapid attenuation. Furthermore, existing mineral insect repellent patches have relatively limited functions, typically only emphasizing insect repellency, making it difficult to simultaneously achieve an integrated effect of insect prevention, moth prevention, mildew prevention, moisture control, and wardrobe air purification.

[0006] Micro- and nano-tourmaline, diatomaceous earth, tourmaline, attapulgite, and other natural minerals can continuously ionize to generate hydroxyl anions upon contact with trace amounts of water molecules in the air. These hydroxyl anions possess strong oxidizing activity, capable of destroying the epidermal proteins and respiratory systems of insect eggs and larvae, inhibiting the metabolic activities of mold and mites, and decomposing odor molecules such as formaldehyde, hydrogen sulfide, and sweat odor from clothing. Furthermore, they are non-toxic and leave no residue, making them suitable for long-term use in sealed wardrobes. However, to translate this mechanism into a product that can be used stably for extended periods, three interrelated issues need to be addressed simultaneously: uniform dispersion of micro- and nano-minerals, long-term controlled release of hydroxyl anions, and multi-layered composite moisture protection. Existing products have not yet provided an effective overall solution. Summary of the Invention

[0007] This invention mainly addresses the following two technical problems.

[0008] First, the mineral powder in existing mineral negative ion insect repellent patches has a large particle size, is prone to agglomeration and uneven dispersion, resulting in insufficient release of hydroxyl negative ions, short release cycle, and uncontrollable release rate, with excessively high initial concentration and rapid decay in the later stage.

[0009] Secondly, existing insect-repellent patches lack a moisture-proof and moisture-locking composite structure, making it easy for moisture inside the wardrobe to penetrate the functional layer, causing the mineral powder to become damp, clump together, and become ineffective. At the same time, the product has only one function and cannot simultaneously achieve insect prevention, moth prevention, mildew prevention, moisture prevention, and odor removal and purification.

[0010] In addition, traditional chemical insect repellents are toxic and irritating, and have a short duration of effect. Natural spice packets can only repel insects but cannot kill insect eggs, which are also problems that this invention overcomes.

[0011] To address the aforementioned problems, this invention provides a micro-nano mineral hydroxyl negative ion wardrobe insect-repellent and moth-proof patch. This insect-repellent and moth-proof patch consists of a breathable, slow-release surface layer, a micro-nano mineral functional core layer, a moisture-proof and water-locking bottom layer, and an adhesive release layer, forming a four-layer integrated structure from the outside in. The micro-nano mineral functional core layer is the core functional layer, composed of micro-nano composite mineral powder, natural plant-based binding fibers, slow-release moisturizing agents, dispersing stabilizers, and breathable pore-regulating agents mixed and pressed according to their respective weight proportions.

[0012] The micro / nano composite mineral powder is composed of tourmaline, diatomaceous earth, tourmaline, and attapulgite in a mass ratio of 3:2:3:2. The particle size is controlled between 200 and 600 nm, and the powder undergoes calcination activation and surface modification with a silane coupling agent. Calcination activation removes impurities from the mineral pores and improves their surface activity; the silane coupling agent forms an organic coating layer on the surface of the mineral particles, improving the interfacial compatibility between the particles and the fiber carrier, preventing particle agglomeration, and enabling uniform dispersion in the fiber pores. Among the composite minerals, tourmaline and tourmaline have the ability to spontaneously polarize and ionize water molecules, while diatomaceous earth and attapulgite have a porous adsorption structure. The synergistic effect of these four elements ensures the continuous generation of hydroxyl anions and is also beneficial for adsorbing odor molecules.

[0013] Natural plant-based binding fibers serve as the supporting framework for mineral powders. They are made from a blend of softwood pulp fibers and corn starch fibers, without the use of chemical adhesives. The interwoven fibers form interconnected, breathable micropores that not only support the mineral powders but also allow hydroxyl negative ions and trace amounts of moisture to slowly permeate outwards, while simultaneously keeping the body soft and flexible.

[0014] The sustained-release moisturizing agent is a compound of glycerin, sodium alginate, and porous maifanite microspheres. It is used to stably maintain trace amounts of moisture within the core layer, providing stable humidity conditions for the continuous ionization of water molecules by the minerals and preventing release interruption due to insufficient moisture in dry environments. The dispersing stabilizer uses modified carboxymethyl cellulose to ensure uniform dispersion of micro / nano mineral powders in the slurry and molded core layer, preventing functional failure caused by localized agglomeration. The air permeability porosity regulator uses biodegradable microcrystalline cellulose microparticles to control the porosity of the core layer, allowing hydroxyl anions to be released at a relatively uniform rate, avoiding excessively high release concentrations in a short period.

[0015] The four-layer structure each serves a different function. The breathable, slow-release surface layer is made of ultra-thin, breathable non-woven fabric, allowing hydroxyl negative ions and moisture to escape while preventing mineral dust from leaking out and contaminating clothing. The micro-nano mineral functional core layer is the functional layer that generates hydroxyl negative ions. The moisture-proof and water-locking bottom layer is a one-way breathable and waterproof membrane that prevents condensation from the wardrobe's inner walls from seeping back into the core layer, while allowing trace amounts of moisture inside the core layer to evaporate, maintaining a suitable humidity level without being soaked in liquid water. The adhesive release layer consists of water-based pressure-sensitive adhesive and silicone release film. When in use, simply peel off the release film to directly adhere it to the wardrobe shelves, doors, or the inside of storage boxes. When not in use, the release film remains sealed to prevent the functional layers from prematurely contacting air and becoming damaged.

[0016] Based on the above-mentioned basic solution, the present invention also provides the following further technical solutions.

[0017] In one embodiment, the calcination activation temperature of the micro-nano composite mineral powder is 420–480°C, and the amount of silane coupling agent added is 2.5% of the total mass of the mineral powder, so as to balance the activation effect and the uniformity of modification.

[0018] In one embodiment, the micro-nano composite mineral powder is composed of 30 parts by weight of tourmaline, 20 parts by weight of diatomaceous earth, 30 parts by weight of tourmaline, and 20 parts by weight of attapulgite. This ratio corresponds to a mass ratio of 3:2:3:2, which facilitates the batching process.

[0019] In one embodiment, the raw material ratio of the functional core layer is 55 parts of micro-nano composite mineral powder, 26 parts of natural plant bonding fiber, 12 parts of slow-release moisturizing agent, 4 parts of dispersing stabilizer, and 3 parts of air-permeable pore regulator, so that the mineral loading, fiber skeleton strength and pore control ability are balanced.

[0020] In one embodiment, the slow-release moisturizing agent is a compound of glycerin, sodium alginate and maifanite microspheres in a mass ratio of 2:1:3. Glycerin and sodium alginate provide water-locking and moisturizing effects, while maifanite microspheres utilize their porous structure to store water and release it slowly.

[0021] In one embodiment, the micro / nano mineral functional core layer has a thickness of 1.2–2.0 mm and a porosity of 40%–55%; the breathable, slow-release surface layer has a thickness of 0.08–0.12 mm and a pore diameter of 5–20 μm; the moisture-proof and water-locking bottom layer has a water vapor permeability of 500–800 g / (m²·24h), and liquid water cannot permeate back to the core layer. These parameters collectively define the breathability and moisture-proof performance of each layer.

[0022] In one embodiment, the plant-based natural binding fiber is a mixture of coniferous wood pulp fiber and corn starch fiber, with a fiber length of 0.1–0.5 mm; the dispersing stabilizer is modified carboxymethyl cellulose; and the air permeability pore regulator is biodegradable microcrystalline cellulose microparticles.

[0023] In one embodiment, the size of a single insect-proof and moth-proof patch is 10cm×15cm, the total load of micro-nano minerals on a single patch is 1.8~2.5g, and the stable release period of hydroxyl negative ions in a closed wardrobe is not less than 12 months.

[0024] In one embodiment, the insect-repellent and moth-proof patch does not contain camphor, naphthalene, or pyrethroid insect repellents and can be used in sealed storage environments for silk, cashmere, and infant clothing.

[0025] This invention also provides a method for preparing the above-mentioned insect-proof and moth-proof patch, comprising five steps: micro-nano mineral modification pretreatment, functional core layer slurry preparation, wet pressing and drying, four-layer composite hot pressing, and slitting and sealing. First, four minerals are mixed and ball-milled to 200-600 nm, then calcined, activated, and modified with a silane coupling agent to obtain modified mineral powder. Next, the modified mineral powder is mixed with fiber, moisturizing agent, dispersant stabilizer, pore regulator, and water to form a uniform slurry. The slurry is then formed by sheet forming and segmented low-temperature drying to obtain a mineral functional core layer with controlled moisture content. Subsequently, a breathable slow-release surface layer, a mineral functional core layer, and a moisture-proof and water-locking bottom layer are hot-pressed together, and a pressure-sensitive adhesive is rolled onto the back of the bottom layer and a release film is attached. Finally, the patch is slid into individual pieces and vacuum-sealed for independent packaging.

[0026] The beneficial effects of this invention are directly brought about by its various technical features, which correspond one-to-one with the technical problems to be solved.

[0027] First, addressing the issues of mineral powder agglomeration, insufficient release, and uncontrollable release, this invention employs micro-nano compound mineral powder with a particle size of 200–600 nm, which is then activated by calcination and surface modified with a silane coupling agent. Combined with a modified carboxymethyl cellulose dispersant and stabilizer, this ensures that the mineral particles are uniformly dispersed in the fiber pores, preventing agglomeration and allowing for more thorough contact between the minerals and air and trace amounts of moisture. A breathable pore regulator controls the core layer porosity at 40%–55%, and combined with pore control in the breathable, slow-release surface layer, this allows hydroxyl negative ions to be continuously released at a relatively uniform rate. This avoids the problems of excessively high initial concentrations irritating the respiratory tract and rapid failure later, thereby extending the stable release period in a sealed wardrobe.

[0028] Secondly, to address the problem of powder clumping due to moisture intrusion, this invention sets a moisture-proof and water-locking bottom layer inside the functional core layer. This bottom layer is a one-way breathable and waterproof membrane, which prevents liquid water from penetrating back into the core layer, thereby isolating the mineral powder from the erosion caused by condensation on the inner wall of the wardrobe. At the same time, it allows trace amounts of water vapor inside the core layer to evaporate outward, maintaining suitable humidity conditions for ionization in the core layer. The slow-release moisturizing agent maintains trace amounts of moisture in the core layer in a dry environment. The combination of the two ensures that the insect-proof and moth-proof sticker can maintain stable function in both humid and dry environments.

[0029] Third, addressing the issues of toxicity and irritation from chemical insect repellents, the lack of insecticidal ability from natural fragrances, and limited functionality, this invention does not add camphor, naphthalene, or pyrethroid insect repellents. It relies on the oxidative activity of hydroxyl negative ions generated by the ionization of micro-nano minerals to destroy the epidermal proteins of insect eggs and larvae, inhibit mold metabolism, and simultaneously decompose formaldehyde, hydrogen sulfide, and odor molecules such as sweat from clothing. This achieves integrated insect prevention, moth prevention, mildew prevention, and air purification. It is non-corrosive and leaves no chemical residue on silk, cashmere, and infant clothing, and is safe for pregnant women, infants, and people with respiratory sensitivities.

[0030] Fourth, the adhesive release layer allows the insect-repellent and moth-proof stickers to be directly applied to wardrobe shelves, cabinet doors, drawers, storage boxes, or the inside of suitcases, making them convenient to use. When not in use, the release film and vacuum aluminum foil packaging work together to isolate air and moisture, preventing premature damage. The functional core layer uses plant fibers and natural minerals as the main raw materials, making it environmentally friendly after disposal. Attached Figure Description

[0031] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which: Figure 1 This is a schematic diagram of the overall layered cross-sectional structure of the insect-proof and moth-proof patch of the present invention; Figure 2 This is a flowchart illustrating the manufacturing process of the insect-repellent and moth-proof patch of the present invention. Explanation of markings in the diagram: 1-Breathable and slow-release surface layer, 2-Micro-nano mineral functional core layer, 3-Moisture-proof and water-locking bottom layer, 4-Adhesive backing layer, 5-Release film Detailed Implementation

[0032] Embodiments of the present invention are described in detail below. Examples of these embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention.

[0033] As shown in Figure 1, the micro-nano mineral hydroxyl negative ion wardrobe insect-repellent and moth-proof sticker of the present invention consists of, from the outside to the inside, a breathable slow-release surface layer 1, a micro-nano mineral functional core layer 2, a moisture-proof and water-locking bottom layer 3, an adhesive backing layer 4, and a release film 5. The adhesive backing layer 4 and the release film 5 together constitute the adhesive-release layer, giving the product a four-layer integrated composite structure. The breathable slow-release surface layer 1 is located on the side facing the air inside the wardrobe, the moisture-proof and water-locking bottom layer 3 is located on the side facing the inner wall of the wardrobe, the adhesive backing layer 4 is coated on the back of the moisture-proof and water-locking bottom layer 3, and the release film 5 covers the adhesive backing layer 4. In use, the release film 5 is removed, and the insect-repellent and moth-proof sticker is adhered to the inner wall or partition of the wardrobe through the adhesive backing layer 4.

[0034] The breathable, slow-release surface layer 1 uses ultra-thin breathable non-woven fabric with a thickness of 0.08–0.12 mm and a pore diameter of 5–20 μm. This layer allows hydroxyl negative ions and water vapor to permeate unidirectionally outwards into the cabinet space, while simultaneously sealing mineral dust within the core layer to prevent dust from falling and contaminating clothing. The micro-nano mineral functional core layer 2 has a thickness of 1.2–2.0 mm and a porosity of 40%–55%, and is the core functional layer for generating hydroxyl negative ions. The moisture-proof and water-locking bottom layer 3 uses a microporous PE breathable and moisture-proof membrane with a unidirectional breathable structure. Its water vapor permeability is 500–800 g / (㎡・24h), allowing gaseous water vapor to escape from the core layer, but preventing liquid water condensed on the cabinet wall from seeping back into the core layer. The adhesive layer 4 uses environmentally friendly water-based pressure-sensitive adhesive, and the release film 5 uses silicone paper.

[0035] Inside the micro / nano mineral functional core layer 2, natural plant bonding fibers intertwine to form a three-dimensional fiber network. Micro / nano composite mineral powder adheres to and fills the pores formed by the interwoven fibers, while interconnected, breathable micropores remain between the fiber networks. This structure, on the one hand, supports the mineral powder through the fibers, and on the other hand, allows air and trace amounts of moisture to enter the core layer and contact the minerals through the interconnected, breathable micropores, facilitating the outward diffusion of generated hydroxyl negative ions. A dispersing stabilizer ensures that the micro / nano composite mineral powder is evenly distributed in the form of single particles or small aggregates, avoiding localized dense agglomeration of powder or blank areas devoid of powder. A porosity regulator occupies a certain space during the molding process and forms controlled pores after drying, thereby adjusting the core layer porosity to 40%–55%.

[0036] The working principle of this invention's insect-repellent and moth-proof patch is as follows: Tourmaline and micro-nano composite mineral powder possess a spontaneously polarized electric field. When trace amounts of water molecules in the air come into contact with the surface of the mineral particles, they ionize under the influence of the electric field, generating hydroxyl negative ions. A slow-release moisturizing agent maintains trace amounts of moisture within the core layer, allowing the ionization process to continue uninterrupted. The generated hydroxyl negative ions diffuse through interconnected breathable micropores to the breathable slow-release surface layer 1 under the influence of the concentration difference, and then enter the wardrobe's internal space through the surface pores. Hydroxyl negative ions have strong oxidizing activity, capable of oxidizing and destroying the eggshell protein and larval epidermal protein of clothes moths, silverfish, and mites, interfering with their respiratory system and metabolic activities, thereby inhibiting pest reproduction; simultaneously, they can inhibit the metabolism of molds such as Aspergillus niger and white mold, and undergo oxidative decomposition reactions with odor molecules such as formaldehyde, hydrogen sulfide, and clothing odor. The moisture-proof and water-locking bottom layer 3 blocks the reverse intrusion of liquid water, preventing the mineral powder from becoming damp and clumping, ensuring that the above process continues even in high-humidity environments such as the rainy season.

[0037] When using, affix the insect-repellent and moth-proof stickers to the inner wall or shelves of the wardrobe. Hydroxyl negative ions are released from the surface of the sticker into the interior space of the wardrobe. Multiple stickers can be affixed to the inside of the wardrobe doors, under the shelves, and on the side walls of the drawers, depending on the volume of the wardrobe.

[0038] The preparation method of the insect-proof and moth-proof patch of the present invention is shown in Figure 2, and includes the following steps.

[0039] Step S1, Pretreatment for Micro / Nano Mineral Modification. Tourmaline, diatomaceous earth, tourmaline, and attapulgite are weighed and mixed in a mass ratio of 3:2:3:2, and then ball-milled until the powder particle size is 200–600 nm. The ball-milled powder is then calcined and activated at 420–480 °C for 1.5–2.5 h to remove pore impurities and improve surface activity. After cooling, a silane coupling agent is added and stirred at high speed for surface modification. The amount of silane coupling agent added is 2.5% of the total mass of the mineral powder. After modification, the powder is filtered and dried to obtain modified micro / nano composite mineral powder.

[0040] Step S2: Preparation of functional core layer slurry. Weigh the modified micro / nano composite mineral powder, natural plant binder fiber, slow-release moisturizing agent, dispersant stabilizer, and air-permeable pore regulator according to weight proportions. Add deionized water and stir at high speed to prepare a uniform, non-agglomerated fiber mineral slurry. The slurry solid content is controlled at 38%–45%. The natural plant binder fiber is a mixture of softwood pulp fiber and corn starch fiber with a length of 0.1–0.5 mm; the slow-release moisturizing agent is a compound of glycerol, sodium alginate, and maifanite microspheres in a mass ratio of 2:1:3; the dispersant stabilizer is modified carboxymethyl cellulose; and the air-permeable pore regulator is biodegradable microcrystalline cellulose microparticles.

[0041] Step S3, wet pressing and drying. The pulp is fed to the paper forming machine and rolled to obtain a wet core blank; low-temperature hot air staged drying is used, with drying temperatures successively at 60℃, 80℃, and 100℃, controlling the moisture content of the core layer after drying to 6%–9%; the core layer is then cut to standard dimensions to obtain mineral functional core layers. Staged drying gradually increases the temperature from low to high to avoid the surface from forming a crust too quickly, preventing internal moisture from being trapped.

[0042] Step S4, four-layer composite hot pressing. The breathable slow-release surface layer, mineral functional core layer and moisture-proof and water-locking bottom layer are unwound from top to bottom and hot-pressed at low temperature at 110-130℃ and 0.3-0.5MPa to combine the three layers into one; environmentally friendly water-based pressure-sensitive adhesive is roller-coated on the back of the moisture-proof and water-locking bottom layer, and a silicone release film is attached to form an adhesive release layer.

[0043] Step S5: Slitting and Individual Sealing. The composite substrate is slitting into standard single pieces and individually sealing them in vacuum aluminum foil bags to isolate them from air and moisture. Disinfection and testing are completed before leaving the factory.

[0044] Seven examples and one comparative example are given below. In each example, the mineral compound ratio is tourmaline, diatomite, tourmaline and attapulgite in a mass ratio of 3:2:3:2. The amount of silane coupling agent added is 2.5% of the total mass of mineral powder. The main differences are in the raw material ratio of the functional core layer, the particle size of the mineral powder and the calcination process parameters.

[0045] Table 1 shows the raw material ratios for the functional core layers in each embodiment.

[0046]

[0047] Table 2 shows the key process parameters for each embodiment.

[0048]

[0049] Example 1 (Baseline formulation, with measured data): Prepared according to the parameters listed in Tables 1 and 2. 30 kg of tourmaline, 20 kg of diatomaceous earth, 30 kg of tourmaline, and 20 kg of attapulgite were weighed in a mass ratio of 3:2:3:2, mixed, and ball-milled to an average particle size of 400 nm. The mixture was calcined and activated at 450 °C for 2 h. After cooling, 2.5% of a silane coupling agent (by mass of the total mineral powder) was added and the mixture was stirred at high speed for modification. The mixture was then filtered and dried to obtain modified micro / nano composite mineral powder. 55 parts by weight of the modified mineral powder, 26 parts by weight of a mixture of softwood pulp fiber and corn starch fiber, 12 parts by weight of a glycerol / sodium alginate / maifanite microsphere compound moisturizing agent, 4 parts by weight of modified carboxymethyl cellulose, and 3 parts by weight of microcrystalline cellulose microparticles were added and stirred at high speed for 30 min to achieve a uniform slurry with a solid content of 42%. The slurry is formed by papermaking and dried in stages at 60℃→80℃→100℃, controlling the moisture content of the core layer to 6%~9%. It is then hot-pressed with a breathable slow-release surface layer and a moisture-proof and water-locking bottom layer at 120℃ and 0.4MPa, coated with water-based pressure-sensitive adhesive by roller and laminated with a release film. It is then cut into 10cm×15cm single sheets with a mineral loading of 2.2g per sheet and sealed in vacuum aluminum foil bags.

[0050] Tests showed that, under normal temperature and sealed wardrobe conditions, the product in this embodiment maintained a stable release period of hydroxyl negative ions for up to 13 months; it achieved a 98.6% kill rate against clothes moth eggs, a 99.1% inhibition rate against wardrobe mold, and a 72% formaldehyde decomposition efficiency. No dust shedding or irritating odor was observed during use. These test results are based on normal temperature and sealed wardrobe conditions and do not apply to long-term open ventilation or extreme temperature and humidity conditions.

[0051] Example 2 (Low Mineral Load): The difference from Example 1 lies in the different proportions of the functional core layer raw materials, as detailed in Table 1. This example has a lower mineral load, a correspondingly higher proportion of fiber and moisturizing agents, and a slightly increased core layer porosity of 50%. It is suitable for scenarios with low insect infestation pressure, such as simple rental wardrobes. The design target is a release period of approximately 10 months, achieving basic insect and mildew prevention standards, with relatively low raw material costs. The release period and cost data for this example are design targets and require further verification data under unified testing conditions.

[0052] Example 3 (High Mineral Load): The difference from Example 1 lies in the different proportions of the functional core layer raw materials, as detailed in Table 1. This example has a higher mineral load, a lower fiber ratio, and an increased core layer thickness of 1.8 mm. It is suitable for wardrobes in the humid rainy season in southern regions or wardrobes with severe insect infestations. The design target is a release period of 15 months, and its effectiveness remains to be verified.

[0053] Example 4 (lower particle size limit 200 nm): The difference from Example 1 is that the average particle size of the mineral powder is 200 nm, which is the lower limit of the particle size range defined in the claims. The smaller particle size increases the specific surface area of ​​the mineral, increasing the contact sites with air and trace water molecules, which is beneficial for increasing the initial release concentration of hydroxyl anions; at the same time, the smaller particles fill the fiber pores more densely, slightly increasing the core porosity to 50%. This example is an alternative implementation method, and its long-term release stability and powder agglomeration risk still need to be verified.

[0054] Example 5 (Particle size limit 600nm): The difference from Example 1 is that the average particle size of the mineral powder is 600nm, which is the upper limit of the particle size range defined in the claims. The larger particle size reduces the specific surface area of ​​the mineral, the release rate of hydroxyl anions tends to be slower, and the core porosity slightly decreases to 46%, which is beneficial for maintaining a longer release cycle in a dry environment. This example is an alternative implementation method, and its release cycle and insect and mildew prevention effects still need to be verified.

[0055] Example 6 (calcination lower limit 420℃ / 2.5h): The difference from Example 1 is that the calcination activation temperature is 420℃ and the calcination time is 2.5h, which is the lower limit of the calcination temperature range defined in the claims, combined with a longer holding time. Extending the holding time at a lower temperature removes mineral porosity impurities and activates the surface in a gentler manner, reducing the impact of high temperature on the mineral crystal structure. This example is an alternative implementation method, and its mineral activation degree and negative ion release performance still need to be verified.

[0056] Example 7 (Calcination upper limit 480℃ / 1.5h): The difference from Example 1 is that the calcination activation temperature is 480℃ and the calcination time is 1.5h, which is the upper limit of the calcination temperature range defined in the claims, combined with a shorter holding time. At higher temperatures, impurities decompose more completely, but the holding time is correspondingly shortened to avoid excessive sintering of mineral particles. This example is an alternative implementation method, and its mineral surface activity and powder dispersibility still need to be verified.

[0057] Comparative Example: A commercially available micron-sized mineral insect repellent patch was used. The mineral powder particles were approximately 10μm in diameter, without surface modification by silane coupling agents, and consisted of a single-layer non-woven fabric structure without a moisture-proof and water-locking bottom layer. Testing revealed that its hydroxyl negative ion release period was only 2.5 months, the mineral powder clumped when damp, the insect egg kill rate was less than 62%, and its function deteriorated after 30 days in a humid environment.

[0058] Table 3 shows a performance comparison between Examples 1 to 7 and the comparative examples.

[0059]

[0060] Example 1: The stable release period of hydroxyl negative ions is 13 months (tested), the killing rate of clothes moth eggs is 98.6% (tested), the mold inhibition rate is 99.1% (tested), the formaldehyde decomposition efficiency is 72% (tested), there is no dust shedding, and the moisture-proof performance is that liquid water cannot penetrate.

[0061] Example 2: The stable release period of hydroxyl negative ions is about 10 months (design target). The insect and mildew prevention performance meets the design target. Dust shedding is expected to be zero. The moisture-proof performance is that liquid water cannot penetrate. The data is yet to be verified.

[0062] Example 3: The stable release period of hydroxyl negative ions is about 15 months (design target), which is suitable for high humidity and pest infestation environments (design target). Dust shedding is expected to be zero, and the moisture-proof performance is that liquid water cannot penetrate. The data is yet to be verified.

[0063] Example 4: The mineral particle size is 200nm. The initial release concentration is designed to be at a relatively high level. The long-term stability needs to be verified. The moisture-proof performance is that liquid water cannot penetrate it.

[0064] Example 5: The mineral particle size is 600nm, the release rate is designed to be relatively slow, the release cycle is designed to be relatively long, the insect and mildew prevention effect is yet to be verified, and the moisture-proof performance is that liquid water does not penetrate.

[0065] Example 6: Calcination temperature 420℃, time 2.5h. The degree of mineral activation and negative ion release performance need to be verified. The moisture-proof performance is that liquid water does not penetrate.

[0066] Example 7: Calcination temperature 480℃, time 1.5h, mineral surface activity and powder dispersibility need to be verified, moisture resistance is that liquid water does not penetrate.

[0067] Comparative example: The stable release period of hydroxyl negative ions is 2.5 months (tested), the insect egg killing rate is less than 62% (tested), and the moisture-proof performance is that the powder clumps when damp, and the function degrades after 30 days in a humid environment.

[0068] As shown in Table 3, Example 1 outperformed the comparative example in terms of release cycle, insect egg kill rate, mold inhibition rate, and moisture-proof performance. Examples 2 to 7 selected different values ​​within the scope of the claims for mineral loading, powder particle size, and calcination process parameters, respectively, covering the differentiated needs of different usage scenarios for the performance of insect-proof and moth-proof patches; their performance data are design targets and still need to be verified under unified testing conditions. The specific thickness, porosity, raw material content, and process parameters of each layer can be adjusted within the range defined by this invention according to the wardrobe volume and the humidity of the usage environment. As long as it adopts a four-layer composite structure consisting of a breathable slow-release surface layer, a micro-nano mineral functional core layer, a moisture-proof and water-locking bottom layer, and an adhesive release layer, and adopts a 200-600nm tourmaline, diatomaceous earth, tourmaline, and attapulgite compound mineral functional core layer modified by calcination activation and silane coupling agent, it falls within the protection scope of this invention.

[0069] Although embodiments of the invention have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.

Claims

1. A micro-nano mineral hydroxyl negative ion wardrobe insect-repellent and moth-proof sticker, characterized in that: The structure consists of four integrated layers from the outside to the inside: a breathable and slow-release surface layer, a micro-nano mineral functional core layer, a moisture-proof and water-locking bottom layer, and an adhesive release layer. The micro-nano mineral functional core layer is made by mixing and pressing the following raw materials in parts by weight: 45-65 parts of micro-nano composite mineral powder, 20-30 parts of natural plant bonding fiber, 8-15 parts of slow-release moisturizing agent, 2-5 parts of dispersing stabilizer, and 1-3 parts of breathable pore regulator. The micro-nano composite mineral powder is made by compounding tourmaline, diatomaceous earth, tourmaline, and attapulgite in a mass ratio of 3:2:3:2, with a particle size of 200-600 nm, and is treated with calcination activation and surface modification with silane coupling agent.

2. The micro-nano mineral hydroxyl negative ion wardrobe insect-proof and moth-proof sticker according to claim 1, characterized in that, The calcination activation temperature of the micro-nano composite mineral powder is 420-480℃, and the amount of silane coupling agent added is 2.5% of the total mass of the mineral powder.

3. The micro-nano mineral hydroxyl negative ion wardrobe insect-proof and moth-proof sticker according to claim 1, characterized in that, The micro-nano composite mineral powder is composed of 30 parts by weight of tourmaline, 20 parts by weight of diatomite, 30 parts by weight of tourmaline, and 20 parts by weight of attapulgite.

4. The micro-nano mineral hydroxyl negative ion wardrobe insect-proof and moth-proof sticker according to claim 1, characterized in that, The raw material ratio of the micro-nano mineral functional core layer is as follows: 55 parts micro-nano composite mineral powder, 26 parts natural plant bonding fiber, 12 parts slow-release moisturizing agent, 4 parts dispersing stabilizer, and 3 parts air permeability pore regulator.

5. The micro-nano mineral hydroxyl negative ion wardrobe insect-proof and moth-proof sticker according to claim 1, characterized in that, The sustained-release moisturizing agent is composed of glycerin, sodium alginate and maifanite microspheres in a mass ratio of 2:1:

3.

6. The micro-nano mineral hydroxyl negative ion wardrobe insect-proof and moth-proof sticker according to claim 1, characterized in that, The thickness of the micro-nano mineral functional core layer is 1.2–2.0 mm, and the porosity is 40%–55%; the thickness of the breathable slow-release surface layer is 0.08–0.12 mm, and the pore diameter is 5–20 μm; the moisture-proof and water-locking bottom layer is a one-way breathable and waterproof membrane with a water vapor permeability of 500–800 g / (㎡・24h), and liquid water cannot permeate back into the micro-nano mineral functional core layer.

7. The micro-nano mineral hydroxyl negative ion wardrobe insect-proof and moth-proof sticker according to claim 1, characterized in that, The plant-based natural bonding fiber is a mixture of coniferous wood pulp fiber and corn starch fiber, with a fiber length of 0.1–0.5 mm; the dispersing stabilizer is modified carboxymethyl cellulose; and the air permeability pore regulator is biodegradable microcrystalline cellulose microparticles.

8. The micro-nano mineral hydroxyl negative ion wardrobe insect-proof and moth-proof sticker according to claim 1, characterized in that, Each insect-repellent and moth-proof patch measures 10cm x 15cm, with a total micro-nano mineral load of 1.8–2.5g per patch. The stable release period of hydroxyl negative ions in a closed wardrobe is no less than 12 months.

9. The micro-nano mineral hydroxyl negative ion wardrobe insect-proof and moth-proof sticker according to claim 1, characterized in that, The insect-repellent and moth-proof patch does not contain camphor, naphthalene, or pyrethroid insecticides and is suitable for sealed storage environments for silk, cashmere, and infant clothing.

10. A method for preparing a micro / nano mineral hydroxyl negative ion wardrobe insect-repellent and moth-proof patch as described in any one of claims 1 to 9, characterized in that, It includes the following steps: S1, Micro-nano mineral modification pretreatment: Tourmaline, diatomaceous earth, tourmaline and attapulgite are mixed and ball-milled to a particle size of 200-600 nm, calcined and activated at 420-480℃ for 1.5-2.5 h, cooled and then silane coupling agent is added and stirred at high speed for surface modification. After filtration and drying, modified micro-nano composite mineral powder is obtained. S2, Functional core layer slurry preparation: Mix the modified micro-nano composite mineral powder, natural plant bonding fiber, slow-release moisturizing agent, dispersing stabilizer and air permeability pore regulator according to the weight parts, add deionized water and stir to prepare a uniform slurry with a solid content of 38% to 45%. S3, wet pressing and drying: the slurry is formed into a wet core blank, dried in stages at low temperature with hot air, and the moisture content of the core layer is controlled to be 6% to 9%. The core layer is then cut to obtain the mineral functional core layer. S4, four-layer composite hot pressing: the breathable slow-release surface layer, the mineral functional core layer and the moisture-proof and water-locking bottom layer are stacked in sequence and hot-pressed at 110~130℃ and 0.3~0.5MPa. After the water-based pressure-sensitive adhesive is rolled onto the back of the moisture-proof and water-locking bottom layer, the silicone paper release layer is bonded on. S5, Slitting and Sealing: The composite substrate is slitting into individual finished products and then individually sealed in aluminum foil vacuum packaging.

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