Antibacterial anti-mite low odor slow resilience memory sponge

Abstract

The application discloses an antibacterial and anti-mite low-odor slow-rebound memory sponge, relates to the technical field of high polymer foam materials, and adopts in-situ doping and synchronous grafting coupling technology of an antibacterial and anti-mite active group to uniformly disperse mesoporous silicon dioxide nanoparticles in a polyurethane matrix and realize in-situ anchoring when the slow-rebound memory sponge is foamed and formed, and simultaneously graft non-dissolution type antibacterial and anti-mite active groups on the surface of the mesoporous silicon dioxide; the mesoporous silicon dioxide continuously adsorbs trace volatile odor molecules in the sponge by virtue of a high specific surface area, realizes static odor locking and odor removal, the antibacterial and anti-mite groups are stably combined by a covalent bond without migration and precipitation risk, the mesoporous structure blocks a moist microenvironment for mites to inhabit, and bacteria breeding is inhibited from the source, so that the sponge has both persistent antibacterial and anti-mite performance and ultralow odor release characteristics without the need of adding covering type fragrances and free antibacterial additives.

Description

Technical Field

[0001] This invention relates to the field of polymer foam materials technology, specifically to an antibacterial, anti-mite, low-odor, slow-rebound memory foam. Background Technology

[0002] Slow rebound memory foam, also known as temperature-sensitive memory foam, is a viscoelastic polyurethane foam material. With its slow rebound, conforming to the human body contour, and pressure dispersion properties, slow rebound memory foam is widely used in various comfort products such as home mattresses, pillows, medical care products, and automotive interiors. It plays an important role in improving the comfort of product use, meets people's pursuit of a high-quality life, and has broad market application prospects.

[0003] However, traditional slow-rebound memory foam has many obvious performance defects. First, its porous structure and large surface area make it highly susceptible to absorbing moisture and dust from the air, leading to the growth of bacteria and mites. This can cause health problems such as skin allergies and respiratory discomfort, seriously affecting safety and posing a potential threat to user health. Second, in the traditional memory foam manufacturing process, unreacted monomers may remain in the raw materials such as polyether polyols, isocyanates, and catalysts. Additionally, some additives are volatile and release irritating odors. Long-term exposure to this environment can harm human health and reduce the user experience. Third, existing antibacterial and anti-mite... Modification technologies often employ the addition of a single antibacterial agent, which not only has limited antibacterial and anti-mite effects and poor durability, but also easily leads to a decrease in the slow rebound performance of the sponge, resulting in problems such as excessively fast rebound speed and uneven pressure distribution. It is difficult to achieve a balance between antibacterial and anti-mite properties, low odor, and excellent slow rebound performance. Fourthly, some antibacterial and anti-mite sponges rely on free antibacterial additives or masking fragrances. Free antibacterial additives are prone to migration and precipitation, and their antibacterial and anti-mite effects decrease after long-term use, and they also pose safety hazards. Masking fragrances cannot eliminate odors from the source, but can only temporarily cover them up, which can easily cause secondary odor pollution and fail to meet consumers' requirements for product safety and environmental protection. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of existing technologies and provide an antibacterial, anti-mite, low-odor, slow-rebound memory foam. This foam utilizes a technology that combines in-situ doping of mesoporous silica with simultaneous grafting and coupling of antibacterial and anti-mite active groups. During the foaming process, mesoporous silica nanoparticles are uniformly dispersed within a polyurethane matrix and anchored in situ. Simultaneously, non-leaching antibacterial and anti-mite active groups are grafted onto the surface of the mesoporous silica. The high specific surface area of ​​the mesoporous silica allows for the continuous adsorption of trace volatile odor molecules within the foam, achieving static odor locking and removal. The antibacterial and anti-mite groups are stably bound by covalent bonds, eliminating the risk of migration and precipitation. This design not only blocks the humid microenvironment where mites reside due to its mesoporous structure but also inhibits bacterial growth at its source. No masking fragrances or free antibacterial additives are needed, giving the foam both long-lasting antibacterial and anti-mite properties and ultra-low odor release characteristics.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: an antibacterial, anti-mite, low-odor, slow-rebound memory foam, which is composed of the following raw materials by weight: Slow-rebound polyether polyol: 60-80 parts; Polymer polyol: 10-20 parts; Isocyanate: 45-60 parts; Mesoporous silica-based composite antibacterial and anti-mite agent: 1.0-2.5 parts; Low-odor catalyst: 0.5-1.2 parts; Foam stabilizer: 0.3-0.8 parts; Foaming agent: 1.5-3.0 parts; Deodorizer: 0.3-1.0 parts; Crosslinking agent: 0.2-0.5 parts; Grafting accelerator: 0.1-0.3 parts; The slow-rebound polyether polyol is a highly active polyether polyol with a hydroxyl value of 28-35 mgKOH / g and a molecular weight distribution of 2000-4000. The polymer polyol is white oil POP with a solid content of 30-40%; The isocyanate is a low-free MDI / TDI mixture; The mesoporous silica-based composite antibacterial and anti-mite agent is made by simultaneously grafting non-leaching antibacterial groups and mite-repellent active groups onto the surface of mesoporous silica nanoparticles. The low-odor catalyst is prepared by mixing an organic bismuth catalyst and a triethylenediamine derivative in a weight ratio of 2:1.

[0006] Furthermore, the isocyanate is a low-free MDI / TDI mixture, wherein the free MDI content is ≤0.5%, the free TDI content is ≤0.3%, and the weight ratio of MDI to TDI is 3-5:1.

[0007] Furthermore, the mesoporous silica nanoparticles have a particle size of 30-80 nm, a mesopore size of 2-5 nm, and a specific surface area of ​​500-800 m². 2 / g.

[0008] Furthermore, the non-leaching antibacterial group is a quaternary ammonium salt group, the acaricide active group is a plant-derived acaricide group, and the antibacterial group and the acaricide group are covalently grafted onto the surface of mesoporous silica, with a grafting rate of 8-15%.

[0009] Furthermore, the specific preparation method of the mesoporous silica-based composite antibacterial and anti-mite agent is as follows: mesoporous silica nanoparticles are added to anhydrous ethanol and ultrasonically dispersed for 30-60 min. Silane coupling agent KH-570 is added, and the mixture is stirred at a constant temperature of 60-70℃ for 2-3 h. Then, antibacterial monomers, anti-mite monomers, and grafting promoters are added sequentially, and the mixture is reacted at a constant temperature of 75-85℃ for 4-6 h with a stirring speed of 400-600 r / min. The reaction temperature fluctuation is controlled to be ≤2℃. After the reaction is completed, the mixture is centrifuged at 8000-10000 r / min for 10-15 min, the precipitate is collected, washed 3-4 times with anhydrous ethanol, and then vacuum dried at 80-90℃ for 6-8 h to obtain the mesoporous silica-based composite antibacterial and anti-mite agent.

[0010] Furthermore, the amount of the silane coupling agent KH-570 added is 5-8% of the mass of mesoporous silica.

[0011] Furthermore, the amount of antibacterial monomer added is 10-15% of the mass of mesoporous silica; the amount of acaricide added is 8-12% of the mass of mesoporous silica; and the amount of grafting promoter added is 2-3% of the total mass of antibacterial monomer and acaricide.

[0012] Furthermore, the low-odor catalyst is prepared by mixing an organic bismuth catalyst and a triethylenediamine derivative in a weight ratio of 2:1; the foam stabilizer is an organosilicon foam stabilizer, specifically L-3002 or L-580; the foaming agent is prepared by mixing deionized water and cyclopentane in a weight ratio of 3:1; the deodorizing agent is prepared by mixing activated carbon powder and molecular sieve powder in a weight ratio of 1:1; the crosslinking agent is glycerol; and the grafting accelerator is azobisisobutyronitrile.

[0013] Furthermore, the method for preparing the sponge is as follows: Raw material pretreatment: Place the slow rebound polyether polyol and polymer polyol in a constant temperature oven at 40-50℃ and dry for 2-3 hours, controlling the water content to ≤0.05%; grind the mesoporous silica-based composite antibacterial and anti-mite agent and deodorizer evenly for later use; dissolve the grafting accelerator in a small amount of anhydrous ethanol to prepare a diluted solution for later use. Premixing: Add the pretreated slow-rebound polyether polyol and polymer polyol to a high-speed stirring tank, adjust the speed to 800-1000 r / min, stir for 5-8 min, and after mixing evenly, add mesoporous silica-based composite antibacterial and anti-mite agent, deodorizer, low-odor catalyst, foam stabilizer and crosslinking agent in sequence, and add grafting accelerator dilution dropwise at the same time, and continue stirring for 10-15 min; Foaming reaction: Add foaming agent to the obtained mixture, adjust the speed to 1200-1500 r / min, stir for 3-5 min, mix evenly, quickly add isocyanate, continue stirring for 8-12 s, control the isocyanate index in the range of 1.05-1.15, and form a stable mixture composite system. Molding curing: Quickly pour the reaction mixture into a mold preheated to 40-50℃, close the mold, and cure at 45-55℃ and 0.1-0.15MPa for 15-20 minutes before demolding to obtain the crude sponge product; Post-processing: Place the coarse sponge in a constant temperature, humidity and ventilation aging chamber, control the temperature at 50-60℃ and the relative humidity at 40%-50%, and force ventilation for 48-72 hours. After ventilation, cool the sponge to room temperature, cut and trim it to the required size to obtain the finished antibacterial, anti-mite, low-odor, slow-rebound memory foam.

[0014] Compared with existing technologies, this antibacterial, anti-mite, low-odor, slow-rebound memory foam has the following beneficial effects: This invention effectively avoids the safety hazards of antibacterial agent migration and precipitation by covalently grafting non-leaching antibacterial and anti-mite active groups onto the surface of mesoporous silica. Simultaneously, the mesoporous structure blocks the humid environment where mites inhabit, achieving a long-lasting and safe antibacterial and anti-mite effect from the source. Regarding odor control, low-volatility raw materials are selected to reduce odor generation at the source. Combined with the adsorption effect of mesoporous silica and the synergistic effect of the composite deodorizer, ultra-low odor release is achieved, eliminating the need for masking fragrances and solving the problem of secondary odor pollution. In terms of slow rebound performance, by optimizing the raw material ratio, adjusting the cross-linking density, and using a suitable foam stabilizer, a uniform and dense cell structure is formed. The in-situ anchoring of mesoporous silica nanoparticles not only does not affect the viscoelasticity of the sponge but also further enhances its structural stability and rebound reliability. Long-term use is less prone to deformation and rebound failure, conforming to human needs and providing a better user experience.

[0015] Other advantages, objectives and features of the invention will be set forth in part in the description which follows, and in part will be apparent to those skilled in the art from the following examination or study, or may be learned from the practice of the invention. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are merely some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without any creative effort.

[0017] Figure 1 A flowchart illustrating the preparation method of an antibacterial, anti-mite, low-odor, slow-rebound memory foam; Figure 2 A flowchart for an antibacterial, anti-mite, low-odor, slow-rebound memory foam. Detailed Implementation

[0018] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features and effects of the present invention, in conjunction with the accompanying drawings and preferred embodiments, is provided below.

[0019] Example 1 An antibacterial, anti-mite, low-odor, slow-rebound memory foam, composed of the following raw materials by weight: Slow-rebound polyether polyol: 70 parts; Polymer polyol (white oil POP, solid content 35%): 15 parts; Isocyanate (low free MDI / TDI mixture, MDI:TDI=4:1, free MDI≤0.5%, free TDI≤0.3%): 52 parts; Mesoporous silica-based composite antibacterial and anti-mite agent: 1.8 parts; Low-odor catalyst (organic bismuth catalyst KB-16: triethylenediamine derivative A33=2:1): 0.8 parts; Foam stabilizer (L-3002): 0.5 parts; Foaming agent (deionized water: cyclopentane=3:1): 2.2 parts; Deodorizer (coconut shell activated carbon powder: 3A molecular sieve powder=1:1, particle size 150 mesh): 0.7 parts; Crosslinking agent (glycerol): 0.3 parts; Grafting accelerator (AIBN): 0.2 parts.

[0020] like Figure 1 As shown, the slow-rebound polyether polyol and polymer polyol were dried in a constant temperature oven at 45°C for 2.5 hours, and the water content was controlled to be ≤0.05%; the mesoporous silica-based composite antibacterial and anti-mite agent and deodorizing agent were ground evenly and set aside; the grafting accelerator was dissolved in a small amount of anhydrous ethanol to prepare a diluted solution and set aside. Add the pretreated slow-rebound polyether polyol and polymer polyol to a high-speed stirring tank, adjust the speed to 900 r / min, stir for 6 min, and after mixing evenly, add mesoporous silica-based composite antibacterial and anti-mite agent, deodorizer, low-odor catalyst, foam stabilizer and crosslinking agent in sequence, and add grafting accelerator dilution dropwise at the same time, and continue stirring for 12 min to ensure that each component is evenly dispersed. Add a foaming agent to the resulting mixture, adjust the speed to 1300 r / min, stir for 4 min, mix evenly, quickly add isocyanate, continue stirring for 10 s, and control the isocyanate index to 1.1. In this process, the in-situ anchoring of mesoporous silica and the simultaneous grafting of antibacterial and anti-mite groups are achieved. The resulting reaction mixture was quickly poured into a mold preheated to 45°C, the mold was closed, and the mixture was aged at 50°C and 0.12 MPa for 18 minutes. Then the mixture was demolded to obtain the crude sponge product. The coarse sponge is placed in a constant temperature and humidity ventilated aging chamber, with the temperature controlled at 55℃ and the relative humidity at 45%, and forced ventilation for 60 hours. The residual odor is statically adsorbed by the mesoporous silica. After ventilation, the sponge is cooled to room temperature, cut and trimmed to the required size to obtain the finished product.

[0021] Example 2 An antibacterial, anti-mite, low-odor, slow-rebound memory foam, composed of the following raw materials by weight: Slow-rebound polyether polyol (hydroxyl value 28 mg KOH / g, molecular weight 2000, GLR-2000): 60 parts; Polymer polyol (white oil POP, solid content 30%): 10 parts; Isocyanate (low free MDI / TDI mixture, MDI:TDI=3:1, free MDI≤0.5%, free TDI≤0.3%): 45 parts; Mesoporous silica-based composite antibacterial and anti-mite agent: 1.0 part; Low-odor catalyst (organic bismuth catalyst KB-16: triethylenediamine derivative A33=2:1): 0.5 parts; Foam stabilizer (L-580): 0.3 parts; Foaming agent (deionized water: cyclopentane=3:1): 1.5 parts; Deodorizer (coconut shell activated carbon powder: 3A molecular sieve powder=1:1, particle size 100 mesh): 0.3 parts; Crosslinking agent (glycerol): 0.2 parts; Grafting accelerator (AIBN): 0.1 parts.

[0022] like Figure 2 As shown, the slow-rebound polyether polyol and polymer polyol were dried in a constant temperature oven at 40°C for 2 hours, and the water content was controlled to be ≤0.05%; the mesoporous silica-based composite antibacterial and anti-mite agent and deodorizing agent were ground evenly and set aside; the grafting accelerator was dissolved in a small amount of anhydrous ethanol to prepare a diluted solution and set aside. Add the pretreated slow-rebound polyether polyol and polymer polyol to a high-speed stirring tank, adjust the speed to 800 r / min, stir for 5 min, and after mixing evenly, add mesoporous silica-based composite antibacterial and anti-mite agent, deodorizer, low-odor catalyst, foam stabilizer and crosslinking agent in sequence, and add grafting accelerator dilution dropwise at the same time, and continue stirring for 10 min to ensure that each component is evenly dispersed. Add a foaming agent to the obtained mixture, adjust the speed to 1200 r / min, stir for 3 min, mix evenly, quickly add isocyanate, continue stirring for 8 s, control the isocyanate index to 1.05, and achieve in-situ anchoring of mesoporous silica and simultaneous grafting of antibacterial and anti-mite groups during this process. The resulting reaction mixture was quickly poured into a mold preheated to 40°C, the mold was closed, and the mixture was aged at 45°C and 0.1 MPa for 15 minutes. Then the mixture was demolded to obtain the crude sponge product. The coarse sponge is placed in a constant temperature and humidity ventilated aging chamber, with the temperature controlled at 50℃ and the relative humidity at 40%, and forced ventilation for 48 hours. The residual odor is statically adsorbed by the mesoporous silica. After ventilation, the sponge is cooled to room temperature, cut and trimmed to the required size to obtain the finished product.

[0023] Example 3 An antibacterial, anti-mite, low-odor, slow-rebound memory foam, composed of the following raw materials by weight: Slow-rebound polyether polyol (hydroxyl value 35mgKOH / g, molecular weight 4000): 80 parts; Polymer polyol (white oil POP, solid content 40%): 20 parts; Isocyanate (low free MDI / TDI mixture, MDI:TDI=5:1, free MDI≤0.5%, free TDI≤0.3%): 60 parts; Mesoporous silica-based composite antibacterial and anti-mite agent: 2.5 parts; Low-odor catalyst (organic bismuth catalyst KB-16: triethylenediamine derivative A33=2:1): 1.2 parts; Foam stabilizer (L-3002): 0.8 parts; Foaming agent (deionized water: cyclopentane=3:1): 3.0 parts; Deodorizer (coconut shell activated carbon powder: 3A molecular sieve powder=1:1, particle size 200 mesh): 1.0 part; Crosslinking agent (glycerol): 0.5 parts; Grafting accelerator (AIBN): 0.3 parts.

[0024] The slow-rebound polyether polyol and polymer polyol were dried in a constant temperature oven at 50°C for 3 hours, and the water content was controlled to be ≤0.05%. The mesoporous silica-based composite antibacterial and anti-mite agent and deodorizer were ground evenly and set aside. The grafting accelerator was dissolved in a small amount of anhydrous ethanol to prepare a diluted solution and set aside. Add the pretreated slow-rebound polyether polyol and polymer polyol to a high-speed stirring tank, adjust the speed to 1000 r / min, stir for 8 min, and after mixing evenly, add mesoporous silica-based composite antibacterial and anti-mite agent, deodorizer, low-odor catalyst, foam stabilizer and crosslinking agent in sequence, and add grafting accelerator dilution dropwise at the same time, and continue stirring for 15 min to ensure that each component is evenly dispersed. Add a foaming agent to the resulting mixture, adjust the speed to 1500 r / min, stir for 5 min, mix evenly, quickly add isocyanate, continue stirring for 12 s, and control the isocyanate index to 1.15. In this process, in-situ anchoring of mesoporous silica and simultaneous grafting of antibacterial and anti-mite groups are achieved. The resulting reaction mixture was quickly poured into a mold preheated to 50°C, the mold was closed, and the mixture was aged at 55°C and 0.15 MPa for 20 minutes. Then the mixture was demolded to obtain the crude sponge product. The coarse sponge is placed in a constant temperature and humidity ventilated aging chamber, with the temperature controlled at 60℃ and the relative humidity at 50%, and forced ventilation for 72 hours. The residual odor is statically adsorbed by the mesoporous silica. After ventilation, the sponge is cooled to room temperature, cut and trimmed to the required size to obtain the finished product.

[0025] Comparative Example 1 A slow-rebound memory foam has a formula that is basically the same as that of Example 1, except that: no mesoporous silica-based composite antibacterial and anti-mite agent and grafting promoter are added, and instead, 1.4 parts of traditional free composite antibacterial and anti-mite agent (made by mixing nano zinc oxide and cinnamaldehyde in a weight ratio of 3:1) are used. The remaining raw materials, dosages, and preparation methods are the same as those in Example 1.

[0026] Specific formulation (by weight): Slow-rebound polyether polyol (hydroxyl value 30mgKOH / g, molecular weight 3000): 70 parts; Polymer polyol (white oil POP, solid content 35%): 15 parts; Isocyanate (low free MDI / TDI mixture, MDI:TDI=4:1, free MDI≤0.5%, free TDI≤0.3%): 52 parts; Traditional free-type composite antibacterial and anti-mite agent (nano zinc oxide: cinnamaldehyde=3:1): 1.4 parts; Low-odor catalyst (organic bismuth catalyst KB-16: triethylenediamine derivative A33=2:1): 0.8 parts; Foam stabilizer (L-3002): 0.5 parts; Foaming agent (deionized water: cyclopentane=3:1): 2.2 parts; Deodorizer (coconut shell activated carbon powder: 3A molecular sieve powder=1:1, particle size 150 mesh): 0.7 parts; Crosslinking agent (glycerol): 0.3 parts.

[0027] The preparation method is the same as in Example 1, except that the pretreatment step of the grafting promoter is omitted, and a traditional free composite antibacterial and anti-mite agent is added in the premixing stage to replace the mesoporous silica-based composite antibacterial and anti-mite agent. The remaining steps and parameters remain unchanged.

[0028] Comparative Example 2 A slow-rebound memory foam, with a formula basically the same as that in Example 1, differs in that it uses pure mesoporous silica (particle size 50nm, mesopore size 3-4nm, specific surface area 650m²) without grafted antibacterial and anti-mite groups. 2 The method of replacing the mesoporous silica-based composite antibacterial and anti-mite agent with / g) without changing the amount added, and the other raw materials, dosages, and preparation methods are the same as in Example 1, that is, only mesoporous silica doping is used, and antibacterial and anti-mite active groups are not grafted simultaneously, and the coupling technology of the present invention is not realized.

[0029] Specific formulation (by weight): Slow-rebound polyether polyol (hydroxyl value 30 mg KOH / g, molecular weight 3000): 70 parts; Polymer polyol (white oil POP, solid content 35%): 15 parts; Isocyanate (low free MDI / TDI mixture, MDI:TDI=4:1, free MDI≤0.5%, free TDI≤0.3%): 52 parts; Pure mesoporous silica (particle size 50 nm, mesopore size 3-4 nm, specific surface area 650 m² / g). 2 / g): 1.8 parts; Low-odor catalyst (organic bismuth catalyst KB-16: triethylenediamine derivative A33=2:1): 0.8 parts; Foam stabilizer (L-3002): 0.5 parts; Foaming agent (deionized water: cyclopentane=3:1): 2.2 parts; Deodorizer (coconut shell activated carbon powder: 3A molecular sieve powder=1:1, particle size 150 mesh): 0.7 parts; Crosslinking agent (glycerol): 0.3 parts; Grafting accelerator (AIBN): 0.2 parts.

[0030] The preparation method is the same as in Example 1, except that pure mesoporous silica is used instead of the mesoporous silica-based composite antibacterial and anti-mite agent. The remaining steps and parameters remain unchanged (the grafting promoter is added normally, but since there is no antibacterial and anti-mite group grafting, it only assists in the in-situ anchoring of mesoporous silica and polyurethane matrix).

[0031] Comparative Example 3 A slow-rebound memory foam has a formula that is basically the same as that of Example 1, except that: no mesoporous silica-based composite antibacterial and anti-mite agent, deodorizer and grafting promoter are added, and 1.4 parts of free antibacterial agent (nano zinc oxide) and 0.5 parts of masking fragrance (lemon fragrance) are added. The remaining raw materials and dosages and preparation methods are the same as those of Example 1.

[0032] Specific formulation (by weight): Slow-rebound polyether polyol (hydroxyl value 30mgKOH / g, molecular weight 3000): 70 parts; Polymer polyol (white oil POP, solid content 35%): 15 parts; Isocyanate (low free MDI / TDI mixture, MDI:TDI=4:1, free MDI≤0.5%, free TDI≤0.3%): 52 parts; Free antibacterial agent (nano zinc oxide): 1.4 parts; Low-odor catalyst (organic bismuth catalyst KB-16: triethylenediamine derivative A33=2:1): 0.8 parts; Foam stabilizer (L-3002): 0.5 parts; Foaming agent (deionized water:cyclopentane=3:1): 2.2 parts; Masking fragrance (lemon fragrance): 0.5 parts; Crosslinking agent (glycerin): 0.3 parts.

[0033] The preparation method is the same as in Example 1, except that the pretreatment steps of mesoporous silica-based composite antibacterial and anti-mite agent, deodorizer and grafting promoter are omitted. Free antibacterial agent and masking fragrance are added in the premixing stage, and the remaining steps and parameters remain unchanged.

[0034] Comprehensive performance tests were conducted on the finished sponges prepared in Examples 1-3 and Comparative Examples 1-3. All test samples were finished sponges prepared in each example and comparative example, cut into uniform dimensions (50mm × 50mm × 25mm). Three parallel samples were set for each group of samples, and the average value of the test results was taken. The test environment was uniformly set as follows: temperature 23±2℃, relative humidity 50±5%. The samples were placed in this environment for 24 hours before testing to ensure sample stability. Specific test items, test methods, and operational details are as follows: Antibacterial rate test: Place the sample in a sterile petri dish, inoculate with 0.2 mL of bacterial suspension, spread evenly on the sample surface, cover the petri dish, and incubate for 24 h in a constant temperature incubator at 37±1℃ and 90±5% relative humidity; after incubation, add 10 mL of sterile physiological saline, shake thoroughly to wash, and count the number of colonies using the plate spread method. A blank control group was also set up (no sample added, all other procedures were the same); the antibacterial rate was calculated using the formula: Antibacterial rate (%) = (Number of colonies in blank control group - Number of colonies in sample group) / Number of colonies in blank control group × 100%; Antibacterial rate test after washing: Put the sample into the washing machine, use the standard washing program, dry it after each wash, repeat the washing 50 times, and then test the antibacterial rate using the same method as above.

[0035] Mite prevention rate test: Place the sample in a culture container, add 2 mL of dust mite suspension and an appropriate amount of feed (yeast powder and flour mixed at a ratio of 1:1), seal and place in a constant temperature incubator at 25±2℃ and 75±5% relative humidity for 14 days; after the culture is completed, count the number of surviving dust mites in the container using a dissecting microscope, and set up a blank control group (no sample added, all other operations are the same); the mite prevention rate is calculated as follows: mite prevention rate (%) = (number of surviving dust mites in the blank control group - number of surviving dust mites in the sample group) / number of surviving dust mites in the blank control group × 100%; Mite prevention rate test after washing: Using the same washing method as for antibacterial rate, the sample was washed 50 times and dried, and then the mite prevention rate was tested according to the above method.

[0036] Odor rating test: The sample was cut into 100mm×100mm×25mm pieces and placed at the bottom of a desiccator. It was then placed in an environment of 23±2℃ and 50±5% relative humidity for 24 hours to allow the odor to be fully released. Then, an evaluation team of 5 trained evaluators, in a well-ventilated and odor-free evaluation room, turned on the desiccator and smelled the sample in turn, scoring it against the odor rating standard (Level 1: No odor; Level 2: Slight odor, non-irritating, acceptable; Level 3: Obvious odor, slightly irritating, unacceptable; Level 4: Strong irritating odor, unbearable; Level 5: Extremely strong irritating odor, unbearable). The average score of the 5 evaluators was taken as the final odor rating of the sample, and the average score was rounded to one decimal place to determine the rating.

[0037] Slow rebound time test: Place the sample horizontally on the test platform, adjust the position of the steel ball so that the center of the steel ball is vertically aligned with the center point of the sample surface, release the steel ball and let it fall freely to hit the sample surface. Record the total time required for the steel ball to rebound to the highest point and fall back to the sample surface after the first impact with the sample until it stops rebounding. This is the slow rebound time. Test 5 different points for each sample and take the average value.

[0038] Compression set test: Using a compression set tester, the sample was cut into 25mm×25mm×25mm dimensions, and the initial thickness of the sample was measured (accurate to 0.01mm). Then, the sample was placed in the compression device, the compression rate was adjusted to 50%, and the compression state was fixed. The compression device and the sample were placed together in a constant temperature oven at 70±1℃ for 22 hours. After removal, the compression was immediately released, and the sample was placed in an environment of 23±2℃ and 50±5% relative humidity for 30 minutes. The thickness of the sample after recovery was measured. The formula for calculating compression set is: Compression set (%) = (Initial thickness - Recovery thickness) / Initial thickness × 100%. Three parallel samples were tested for each sample, and the average value was taken.

[0039] VOC content test: The sample was cut into 10mm×10mm×5mm pieces, 1.000g of sample was accurately weighed and placed in a 50mL volumetric flask, 25mL of anhydrous ethanol was added, the flask was sealed and shaken at 23±2℃ for 30min, allowed to stand for 10min, the supernatant was collected, filtered through a 0.45μm filter membrane, and injected into the gas chromatograph for detection; Chromatographic conditions: HP-5 capillary column (30m×0.32mm×0.25μm), initial column temperature of 50℃, held for 2min, then increased to 200℃ at a rate of 10℃ / min, held for 5min; flame ionization detector, detection temperature of 250℃; injection port temperature of 220℃, injection volume of 1μL, carrier gas of nitrogen, flow rate of 1.0mL / min; the total VOC content in the sample was calculated according to the standard curve, and three parallel samples were tested for each sample, and the average value was taken.

[0040] Antimicrobial group migration test: The sample was cut into 50mm×50mm×25mm pieces, the sample mass was accurately weighed, and the sample was placed in a 250mL beaker. 100mL of deionized water was added, and the sample was sealed and shaken at 23±2℃ for 24h. The sample was then removed, and the content of antimicrobial groups in the soaking solution was detected by high performance liquid chromatography (HPLC). If no antimicrobial groups were detected in the soaking solution (detection limit ≤0.01mg / L), it was determined that there was no migration; if antimicrobial groups were detected, it was determined that there was migration. The migration amount was recorded. Three parallel samples were tested for each sample, and the average value was taken. Comparative Example 2 had no antimicrobial groups, and Comparative Example 3 used nano zinc oxide as the antimicrobial agent. The migration was determined by detecting the zinc ion content in the soaking solution.

[0041]

[0042] Based on the above performance test data, it can be seen that the antibacterial, anti-mite, low-odor, slow-rebound memory foam prepared in Examples 1-3 of this invention, thanks to the in-situ doping of mesoporous silica and the simultaneous grafting coupling technology of antibacterial and anti-mite active groups, achieves an antibacterial rate of over 99.5% and an anti-mite rate of ≥99%. Even after 50 washes, it retains over 98% of its antibacterial and anti-mite effects, with no migration of antibacterial groups, demonstrating outstanding safety and durability. The odor level is Grade 1 (virtually odorless), and the VOC content is ≤0.25g / L, meeting the requirements for low odor and low VOC content. The standard ensures no secondary pollution risk; the slow rebound time is controlled within 3-8 seconds, and the compression set is ≤4%. It exhibits excellent structural stability and user experience. Among them, Example 1 achieves the optimal balance between performance and cost in terms of raw material ratio and preparation parameters. It has an antibacterial rate of 99.7% and an antibacterial rate of 98.5% after washing, an anti-mite rate of 99.2% and an anti-mite rate of 98.3% after washing, an odor level of 1, a slow rebound time of 5.2 seconds, a compression set of 3.1%, and a VOC content of 0.21 g / L. All performance characteristics are well-balanced, making it the optimal implementation method.

[0043] Each comparative example exhibits significant performance defects: Comparative Example 1 uses a traditional free antibacterial and anti-mite agent, which initially shows acceptable antibacterial and anti-mite effects, but its performance deteriorates severely after washing, and there is a risk of antibacterial group migration; Comparative Example 2 uses only pure mesoporous silica doped without grafting antibacterial and anti-mite active groups, resulting in extremely poor antibacterial and anti-mite effects that cannot meet usage requirements; Comparative Example 3 uses a free antibacterial agent and masking fragrance, which not only has insufficient antibacterial and anti-mite durability but also causes secondary odor pollution and exceeds VOC content standards.

[0044] The performance defects of the comparative examples further demonstrate that the present invention, through the in-situ doping of mesoporous silica and the simultaneous grafting and coupling technology of antibacterial and anti-mite active groups, effectively solves the technical problems of poor antibacterial and anti-mite effect, insufficient durability, excessive odor, and affected slow rebound performance of slow rebound memory foam in the prior art. The technical solution has significant innovation and practicality, and can be directly applied to large-scale industrial production to meet the high-end use needs of home furnishing, medical, automotive interior and other fields.

[0045] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A type of antibacterial, anti-mite, low-odor, slow-rebound memory foam, characterized in that, By weight, it consists of the following raw materials: Slow-rebound polyether polyol: 60-80 parts; Polymer polyol: 10-20 parts; Isocyanate: 45-60 parts; Mesoporous silica-based composite antibacterial and anti-mite agent: 1.0-2.5 parts; Low-odor catalyst: 0.5-1.2 parts; Foam stabilizer: 0.3-0.8 parts; Foaming agent: 1.5-3.0 parts; Deodorizer: 0.3-1.0 parts; Crosslinking agent: 0.2-0.5 parts; Grafting accelerator: 0.1-0.3 parts; The slow-rebound polyether polyol is a highly active polyether polyol with a hydroxyl value of 28-35 mgKOH / g and a molecular weight distribution of 2000-4000. The polymer polyol is white oil POP with a solid content of 30-40%; The isocyanate is a low-free MDI / TDI mixture; The mesoporous silica-based composite antibacterial and anti-mite agent is made by simultaneously grafting non-leaching antibacterial groups and mite-repellent active groups onto the surface of mesoporous silica nanoparticles. The low-odor catalyst is prepared by mixing an organic bismuth catalyst and a triethylenediamine derivative in a weight ratio of 2:

1.

2. The antibacterial, anti-mite, low-odor, slow-rebound memory foam according to claim 1, characterized in that, The isocyanate is a low-free MDI / TDI mixture, wherein the free MDI content is ≤0.5%, the free TDI content is ≤0.3%, and the weight ratio of MDI to TDI is 3-5:

1.

3. The antibacterial, anti-mite, low-odor, slow-rebound memory foam according to claim 1, characterized in that, The mesoporous silica nanoparticles have a particle size of 30-80 nm, a mesopore size of 2-5 nm, and a specific surface area of ​​500-800 m². 2 / g.

4. The antibacterial, anti-mite, low-odor, slow-rebound memory foam according to claim 1, characterized in that, The non-leaching antibacterial group is a quaternary ammonium salt group, and the mite-repellent active group is a plant-derived mite-repellent group. The antibacterial group and the mite-repellent group are covalently grafted onto the surface of mesoporous silica, with a grafting rate of 8-15%.

5. The antibacterial, anti-mite, low-odor, slow-rebound memory foam according to claim 1, characterized in that, The specific preparation method of the mesoporous silica-based composite antibacterial and anti-mite agent is as follows: Mesoporous silica nanoparticles are added to anhydrous ethanol and ultrasonically dispersed for 30-60 min. Silane coupling agent KH-570 is added, and the mixture is stirred at a constant temperature of 60-70℃ for 2-3 h. Then, antibacterial monomers, anti-mite monomers, and grafting promoters are added sequentially, and the mixture is reacted at a constant temperature of 75-85℃ for 4-6 h with a stirring speed of 400-600 r / min. The reaction temperature fluctuation is controlled to be ≤2℃. After the reaction is completed, the mixture is centrifuged at 8000-10000 r / min for 10-15 min, the precipitate is collected, washed 3-4 times with anhydrous ethanol, and then vacuum dried at 80-90℃ for 6-8 h to obtain the mesoporous silica-based composite antibacterial and anti-mite agent.

6. The antibacterial, anti-mite, low-odor, slow-rebound memory foam according to claim 1, characterized in that, The amount of silane coupling agent KH-570 added is 5-8% of the mass of mesoporous silica.

7. The antibacterial, anti-mite, low-odor, slow-rebound memory foam according to claim 1, characterized in that, The amount of antibacterial monomer added is 10-15% of the mass of mesoporous silica; the amount of acaricide added is 8-12% of the mass of mesoporous silica; and the amount of grafting promoter added is 2-3% of the total mass of antibacterial monomer and acaricide.

8. The antibacterial, anti-mite, low-odor, slow-rebound memory foam according to claim 1, characterized in that, The low-odor catalyst is prepared by mixing an organic bismuth catalyst and a triethylenediamine derivative in a weight ratio of 2:1; the foam stabilizer is an organosilicon foam stabilizer, specifically L-3002 or L-580; the foaming agent is prepared by mixing deionized water and cyclopentane in a weight ratio of 3:1; the deodorizing agent is prepared by mixing activated carbon powder and molecular sieve powder in a weight ratio of 1:1; the crosslinking agent is glycerol; and the grafting accelerator is azobisisobutyronitrile.

9. The antibacterial, anti-mite, low-odor, slow-rebound memory foam according to claim 1, characterized in that, The method for preparing the sponge is as follows: Raw material pretreatment: Place the slow rebound polyether polyol and polymer polyol in a constant temperature oven at 40-50℃ and dry for 2-3 hours, controlling the water content to ≤0.05%; grind the mesoporous silica-based composite antibacterial and anti-mite agent and deodorizer evenly for later use; dissolve the grafting accelerator in a small amount of anhydrous ethanol to prepare a diluted solution for later use. Premixing: Add the pretreated slow-rebound polyether polyol and polymer polyol to a high-speed stirring tank, adjust the speed to 800-1000 r / min, stir for 5-8 min, and after mixing evenly, add mesoporous silica-based composite antibacterial and anti-mite agent, deodorizer, low-odor catalyst, foam stabilizer and crosslinking agent in sequence, and add grafting accelerator dilution dropwise at the same time, and continue stirring for 10-15 min; Foaming reaction: Add foaming agent to the obtained mixture, adjust the speed to 1200-1500 r / min, stir for 3-5 min, mix evenly, quickly add isocyanate, continue stirring for 8-12 s, control the isocyanate index in the range of 1.05-1.15, and form a stable mixture composite system. Molding curing: Quickly pour the reaction mixture into a mold preheated to 40-50℃, close the mold, and cure at 45-55℃ and 0.1-0.15MPa for 15-20 minutes before demolding to obtain the crude sponge product; Post-processing: Place the coarse sponge in a constant temperature, humidity and ventilation aging chamber, control the temperature at 50-60℃ and the relative humidity at 40%-50%, and force ventilation for 48-72 hours. After ventilation, cool the sponge to room temperature, cut and trim it to the required size to obtain the finished antibacterial, anti-mite, low-odor, slow-rebound memory foam.

Images