Antibacterial and deodorant insole material and preparation method thereof
By combining the anthranilic acid-syringaldehyde composite carrier with nanosilver, the problem of easy shedding and incomplete protection of antibacterial components in the existing antibacterial insole materials is solved, and the uniform dispersion and continuous release of antibacterial components in the core layer of the insole is achieved, improving the antibacterial durability and deodorization effect.
Patent Information
- Application Number
- CN202510652181.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-20
- Publication Date
- 2025-08-26
AI Technical Summary
Among the existing antibacterial insole materials, the antibacterial components of the surface coating are prone to fall off, and the core layer lacks antibacterial function, resulting in short antibacterial aging and incomplete protection, and microorganisms can penetrate into the interior to reproduce.
The antho-aminobenzoic acid-syringaldehyde composite carrier is used to combine with nanosilver to destroy the microbial cell membrane and enhance the bactericidal permeability efficiency. At the same time, syringaldehyde neutralizes odor molecules, and combines the compatibility agent EVA-g-GMA to improve material compatibility, forming a three-dimensional antibacterial network.
The uniform dispersion and continuous release of antibacterial components in the core layer of the insole is achieved, which improves the antibacterial durability and deodorization effect, reduces the risk of bacterial resistance, and reduces the generation of odors in physical structure.
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Figure BDA0005411416290000081
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of insole materials and relates to an antibacterial and deodorizing insole material and a preparation method thereof.
[0002] Background technology
[0003] During daily exercise, the feet secrete a large amount of sweat, which accumulates inside the shoes, creating a humid environment. This humid environment provides an ideal breeding ground for bacteria (such as Staphylococcus aureus) and fungi (such as Candida albicans), which can easily lead to foot diseases such as athlete's foot and tinea pedis. Currently, most antimicrobial insoles on the market use surface coating technologies, such as silver ion coatings and antimicrobial fabric composites. However, these antimicrobial ingredients are only distributed on the surface of the insoles, while the core materials (such as EVA and PU foam) lack the corresponding antimicrobial properties. This leads to two major problems: First, the antimicrobial effect is short-lived, as the surface coating easily falls off due to friction or sweat, and once it does, the antimicrobial properties are lost. Second, the protection is not complete. Once the insole is damaged or worn, the core material loses its antimicrobial properties, allowing microorganisms to penetrate and multiply inside the insole, causing secondary contamination. Summary of the Invention
[0004] The purpose of the present invention is to provide an antibacterial and deodorizing shoe insole material and a preparation method thereof. The present invention uses an anthranilic acid-syringaldehyde composite carrier to destroy the microbial cell membrane, thereby enhancing the bactericidal penetration efficiency of nanosilver. At the same time, syringaldehyde neutralizes odor molecules, achieving synergistic effects and realizing the integration of the dual functions of "antibacterial and deodorizing".
[0005] The purpose of the present invention can be achieved through the following technical solutions:
[0006] An antibacterial and deodorizing shoe insole material comprises the following components in parts by weight: 82-100 parts of EVA, 11-15 parts of TPU, 4-6 parts of antibacterial material, 3-5 parts of dispersant and 2-3 parts of compatibilizer.
[0007] As a preferred technical solution of the present invention, the preparation of the antibacterial material includes:
[0008] Step 1: In an inert environment, ultrasonically mix anthranilic acid and anhydrous ethanol, add syringaldehyde, heat and mix, centrifuge to remove the solvent, wash, and freeze-dry to obtain a composite carrier;
[0009] Step 2: Place the composite carrier in a silver nitrate solution and anhydrous ethanol and mix them evenly; add the sodium borohydride solution dropwise under vacuum stirring; continue stirring, filter, and rinse with water to obtain an antibacterial material.
[0010] As a preferred technical solution of the present invention, the dispersant is polyvinylpyrrolidone.
[0011] As a preferred technical solution of the present invention, the compatibilizer is EVA-g-GMA, wherein the GMA content is 1.5%; the model of the TPU is Bayer-385S.
[0012] As a preferred technical solution of the present invention, the compatibilizer is EVA-g-GMA, that is, ethylene-vinyl acetate copolymer grafted with glycidyl methacrylate.
[0013] As a preferred technical solution of the present invention, the preparation method of the compatibilizer is an existing technology, specifically, comprising: mixing 50g of EVA and toluene under nitrogen protection, heating to 110°C and stirring for 1.5h, adding 6g of GMA and 1.5g of initiator DCP for a reaction time of 4h, cooling the reaction solution to room temperature, placing it in anhydrous ethanol for precipitation, collecting the product by filtration, washing it with ethanol 4 times to remove unreacted GMA and homopolymer, and drying it in a vacuum drying oven at 60°C to constant weight to obtain a compatibilizer; wherein, preferably, the VA content in the EVA is 40%.
[0014] As a preferred technical solution of the present invention, in step 1, the ultrasonic mixing is performed at a power of 150-200W for 30-40 minutes; the heated mixing is performed by stirring at a temperature of 50-60°C for 4-5 hours; the cleaning is performed three times with anhydrous ethanol; the anthranilic acid is anthranilic acid; and the mass ratio of the anthranilic acid, anhydrous ethanol, and syringaldehyde is 12-15g:60-70mL:6.5-7.5g.
[0015] As a preferred technical solution of the present invention, in step 2, the stirring time is continued for 1.0-1.5h; the mass ratio of the composite carrier, silver nitrate solution, anhydrous ethanol and sodium borohydride solution is 3-5g:6-9mL:300-400mL:30-38mL; the mass fraction of the silver nitrate solution is 1.5%; and the mass fraction of the sodium borohydride solution is 5%.
[0016] As a preferred technical solution of the present invention, a method for preparing an antibacterial and deodorizing insole material is provided, characterized in that the preparation method comprises the following steps: adding EVA, TPU, an antibacterial material, a dispersant and a compatibilizer into a twin-screw extruder, extruding and granulating to obtain the antibacterial and deodorizing insole material.
[0017] Beneficial effects of the present invention:
[0018] The present invention forms a composite carrier by adding nanosilver and anthranilic acid / syringaldehyde, which is then modified with a compatibilizer and evenly dispersed throughout the insole core layer and surface, forming a three-dimensional antimicrobial network. Even if the surface layer wears, the core layer continues to release the nanosilver antimicrobial component. The compatibilizer EVA-g-GMA chemically bonds with the antimicrobial carrier via epoxy groups, preventing the migration and loss of the nanosilver and ensuring that the antimicrobial properties remain stable even in repeated bending and humid environments.
[0019] The present invention uses an anthranilic acid-syringaldehyde composite carrier to destroy the microbial cell membrane and enhance the bactericidal penetration efficiency of nanosilver. At the same time, syringaldehyde neutralizes odor molecules, achieving synergistic effects and realizing the integration of the dual functions of "antibacterial-deodorization". DETAILED DESCRIPTION
[0020] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose of the invention, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.
[0021] Example 1
[0022] An antibacterial and deodorizing insole material comprises the following components by weight: 82 parts of EVA, 11 parts of TPU, 4 parts of antibacterial material, 3 parts of dispersant, and 2 parts of compatibilizer; the dispersant is polyvinylpyrrolidone; the compatibilizer is EVA-g-GMA, wherein the GMA content is 1.5%;
[0023] Wherein, the preparation of the antibacterial material includes:
[0024] Step 1: In a nitrogen environment, o-aminobenzoic acid and anhydrous ethanol were ultrasonically treated at 150W power for 30 minutes, syringaldehyde was added and stirred at 50°C for 4 hours, the solvent was removed by centrifugation, and the mixture was washed three times with anhydrous ethanol and freeze-dried to obtain a composite carrier; the mass ratio of o-aminobenzoic acid, anhydrous ethanol and syringaldehyde was 12g:60mL:6.5g;
[0025] Step 2: Place the composite carrier in a silver nitrate solution and anhydrous ethanol and mix them evenly. Under vacuum stirring, add the sodium borohydride solution dropwise, continue stirring for 1.0 h, filter, and rinse with clean water to obtain an antibacterial material; wherein the mass ratio of the composite carrier, silver nitrate solution, anhydrous ethanol and sodium borohydride solution is 3g:6mL:300mL:30mL; the mass fraction of the silver nitrate solution is 1.5%; the mass fraction of the sodium borohydride solution is 5%.
[0026] A preparation method of an antibacterial and deodorizing insole material comprises the following steps: kneading EVA, TPU, an antibacterial material, a dispersant and a compatibilizer at a rotation speed of 400 rpm / min for 15 minutes, adding the mixture into a twin-screw extruder, and extruding and granulating the mixture at 160° C. to obtain the antibacterial and deodorizing insole material.
[0027] Example 2
[0028] An antibacterial and deodorizing insole material comprises the following components by weight: 86 parts of EVA, 12 parts of TPU, 4.5 parts of antibacterial material, 3.5 parts of dispersant, and 2.2 parts of compatibilizer; the dispersant is polyvinylpyrrolidone; the compatibilizer is EVA-g-GMA, wherein the GMA content is 1.5%;
[0029] Wherein, the preparation of the antibacterial material includes:
[0030] Step 1: In a nitrogen environment, o-aminobenzoic acid and anhydrous ethanol were ultrasonically treated at 162W power for 32 minutes, syringaldehyde was added, and the mixture was stirred at 52°C for 4.2 hours. After centrifugation to remove the solvent, the mixture was washed three times with anhydrous ethanol and freeze-dried to obtain a composite carrier; the mass ratio of o-aminobenzoic acid, anhydrous ethanol and syringaldehyde was 13g:62mL:6.8g;
[0031] Step 2: Place the composite carrier in a silver nitrate solution and anhydrous ethanol and mix evenly. Under vacuum stirring, add sodium borohydride solution dropwise, continue stirring for 1.1 hours, filter, and rinse with clean water to obtain an antibacterial material; wherein the mass ratio of the composite carrier, silver nitrate solution, anhydrous ethanol and sodium borohydride solution is 3.5g:7mL:325mL:32mL; the mass fraction of the silver nitrate solution is 1.5%; the mass fraction of the sodium borohydride solution is 5%.
[0032] A preparation method of an antibacterial and deodorizing insole material comprises the following steps: kneading EVA, TPU, an antibacterial material, a dispersant and a compatibilizer at a rotation speed of 400 rpm / min for 15 minutes, adding the mixture into a twin-screw extruder, and extruding and granulating the mixture at 161° C. to obtain the antibacterial and deodorizing insole material.
[0033] Example 3
[0034] An antibacterial and deodorizing insole material comprises the following components by weight: 91 parts of EVA, 13 parts of TPU, 5 parts of antibacterial material, 4 parts of dispersant, and 2.5 parts of compatibilizer; the dispersant is polyvinylpyrrolidone; the compatibilizer is EVA-g-GMA, wherein the GMA content is 1.5%;
[0035] Wherein, the preparation of the antibacterial material includes:
[0036] Step 1: In a nitrogen environment, o-aminobenzoic acid and anhydrous ethanol were ultrasonically treated at 175W power for 35 minutes, syringaldehyde was added, and the mixture was stirred at 55°C for 4.5 hours. After centrifugation to remove the solvent, the mixture was washed three times with anhydrous ethanol and freeze-dried to obtain a composite carrier; the mass ratio of o-aminobenzoic acid, anhydrous ethanol and syringaldehyde was 13.5g:65mL:7g;
[0037] Step 2: Place the composite carrier in a silver nitrate solution and anhydrous ethanol and mix evenly. Under vacuum stirring, add sodium borohydride solution dropwise, continue stirring for 1.2 hours, filter, and rinse with clean water to obtain an antibacterial material; wherein the mass ratio of the composite carrier, silver nitrate solution, anhydrous ethanol and sodium borohydride solution is 4g:7.5mL:350mL:34mL; the mass fraction of the silver nitrate solution is 1.5%; the mass fraction of the sodium borohydride solution is 5%.
[0038] A preparation method of an antibacterial and deodorizing insole material comprises the following steps: kneading EVA, TPU, an antibacterial material, a dispersant and a compatibilizer at a rotation speed of 400 rpm / min for 15 minutes, adding the mixture into a twin-screw extruder, and extruding and granulating the mixture at 162° C. to obtain the antibacterial and deodorizing insole material.
[0039] Example 4
[0040] An antibacterial and deodorizing insole material comprises the following components by weight: 96 parts of EVA, 14 parts of TPU, 5.5 parts of antibacterial material, 4.5 parts of dispersant, and 2.8 parts of compatibilizer; the dispersant is polyvinylpyrrolidone; the compatibilizer is EVA-g-GMA, wherein the GMA content is 1.5%;
[0041] Wherein, the preparation of the antibacterial material includes:
[0042] Step 1: In a nitrogen environment, o-aminobenzoic acid and anhydrous ethanol were ultrasonically treated at 185W power for 35 minutes, syringaldehyde was added, and the mixture was stirred at 58°C for 4.5 hours. After centrifugation to remove the solvent, the mixture was washed three times with anhydrous ethanol and freeze-dried to obtain a composite carrier; the mass ratio of o-aminobenzoic acid, anhydrous ethanol and syringaldehyde was 14.2g:68mL:7.2g;
[0043] Step 2: Place the composite carrier in a silver nitrate solution and anhydrous ethanol and mix evenly. Under vacuum stirring, add sodium borohydride solution dropwise, continue stirring for 1.5 hours, filter, and rinse with clean water to obtain an antibacterial material; wherein the mass ratio of the composite carrier, silver nitrate solution, anhydrous ethanol and sodium borohydride solution is 4.5g:8.2mL:375mL:36mL; the mass fraction of the silver nitrate solution is 1.5%; the mass fraction of the sodium borohydride solution is 5%.
[0044] A preparation method of an antibacterial and deodorizing insole material comprises the following steps: kneading EVA, TPU, an antibacterial material, a dispersant and a compatibilizer at a rotation speed of 400 rpm / min for 15 minutes, adding the mixture into a twin-screw extruder, and extruding and granulating the mixture at 165° C. to obtain the antibacterial and deodorizing insole material.
[0045] Example 5
[0046] An antibacterial and deodorizing insole material comprises the following components by weight: 100 parts of EVA, 15 parts of TPU, 6 parts of antibacterial material, 5 parts of dispersant, and 3 parts of compatibilizer; the dispersant is polyvinylpyrrolidone; the compatibilizer is EVA-g-GMA, wherein the GMA content is 1.5%;
[0047] Wherein, the preparation of the antibacterial material includes:
[0048] Step 1: In a nitrogen environment, o-aminobenzoic acid and anhydrous ethanol were ultrasonically treated at 200 W power for 40 minutes, syringaldehyde was added, and the mixture was stirred at 60°C for 5 hours. After centrifugation to remove the solvent, the mixture was washed three times with anhydrous ethanol and freeze-dried to obtain a composite carrier; the mass ratio of o-aminobenzoic acid, anhydrous ethanol and syringaldehyde was 15g:70mL:7.5g;
[0049] Step 2: Place the composite carrier in a silver nitrate solution and anhydrous ethanol and mix them evenly. Under vacuum stirring, add the sodium borohydride solution dropwise, continue stirring for 1.5 hours, filter, and rinse with clean water to obtain an antibacterial material; wherein the mass ratio of the composite carrier, silver nitrate solution, anhydrous ethanol and sodium borohydride solution is 5g:9mL:400mL:38mL; the mass fraction of the silver nitrate solution is 1.5%; the mass fraction of the sodium borohydride solution is 5%.
[0050] A preparation method of an antibacterial and deodorizing insole material comprises the following steps: kneading EVA, TPU, an antibacterial material, a dispersant and a compatibilizer at a rotation speed of 400 rpm / min for 15 minutes, adding the mixture into a twin-screw extruder, and extruding and granulating the mixture at 165° C. to obtain the antibacterial and deodorizing insole material.
[0051] Comparative Example 1
[0052] Compared with Example 4, Comparative Example 1 uses aniline instead of anthranilic acid, and the rest are the same.
[0053] Comparative Example 2
[0054] Compared with Example 4, the mass ratio of anthranilic acid and syringaldehyde in Comparative Example 2 is 14.2g:5g, and the rest are the same.
[0055] Comparative Example 3
[0056] Compared with Example 4, the difference in step 2 of Comparative Example 3 is:
[0057] Step 2: Add sodium borohydride solution dropwise to the silver nitrate solution under vacuum stirring, continue stirring for 1.5 hours, add anhydrous ethanol and the composite carrier, mix, filter, and rinse with water to obtain an antibacterial material;
[0058] The remaining components, preparation steps and parameters were the same.
[0059] Comparative Example 4
[0060] Compared with Example 4, Comparative Example 4 uses EVA instead of the compatibilizer, and the rest are the same.
[0061] The antibacterial and deodorizing insole materials prepared in Examples 1-5 and Comparative Examples 1-4 were tested for their antibacterial properties, and the test results are shown in Table 1.
[0062] Antibacterial performance test: GB / T 20944.3-2008 Escherichia coli (Gram-negative bacteria), Staphylococcus aureus (Gram-positive bacteria), test time is 12h.
[0063] Antibacterial durability test: Wash according to AATCC-61-1996, using a fabric washing fastness tester, with a water temperature of 25°C and 45 minutes as one cycle. The antibacterial rate is tested after 30 cycles of washing. The antibacterial rate test method is the same as above to evaluate the antibacterial durability of the antibacterial material.
[0064] Table 1
[0065]
[0066]
[0067] From the test results in Table 1, it can be seen that compared with Comparative Examples 1-4, the antibacterial and deodorizing insole materials prepared in Examples 1-5 of the present invention have excellent antibacterial effects.
[0068] In the antibacterial and deodorizing insole material prepared by the present invention, anthranilic acid condenses with syringaldehyde through its amino group to form a composite carrier. The composite carrier can destroy bacterial cell membranes and inhibit metabolic enzyme activity. At the same time, amino, hydroxyl and carboxyl groups can also serve as reduction sites to generate nanosilver in situ, reducing the easy agglomeration phenomenon during nanosilver generation while promoting the stable loading of nanosilver. The aldehyde group of syringaldehyde forms an imine structure compound through cross-linking to denature bacterial proteins, inhibit biofilm formation and neutralize odor molecules. Nanosilver penetrates bacterial cell membranes, interferes with DNA replication and induces oxidative stress by continuously releasing silver ions, thereby achieving broad-spectrum bactericidal effects. In the synergistic effect, the composite carrier improves the dispersibility and sustained-release effect of nanosilver. Syringaldehyde enhances the penetration efficiency of silver ions after destroying the bacterial structure. Combined with the broad-spectrum bactericidal effect of nanosilver, it synergizes through multiple antibacterial mechanisms to significantly reduce the risk of bacterial resistance. At the same time, it reduces the decomposition of odorous substances by microorganisms through source inhibition. Combined with the aromatic neutralization effect of syringaldehyde, it ultimately achieves efficient and lasting antibacterial and deodorizing functions.
[0069] Compatibilizers can effectively improve the compatibility of TPU and EVA, reduce microporous defects caused by phase separation, inhibit sweat from penetrating the material and breeding bacteria, and reduce odor generation from a physical structural perspective. Furthermore, the epoxy groups of GMA contained in the compatibilizer undergo a ring-opening reaction with the amino groups of TPU and the amino and hydroxyl groups in the composite carrier, forming chemical bonds. This strengthens the interfacial bonding between the EVA matrix and the antimicrobial material, making the nanosilver antimicrobial material more evenly distributed in the EVA / TPU blend system and reducing agglomeration, thereby increasing the specific surface area and sustained-release efficiency of the nanosilver. Through chemical bonding, GMA anchors the nanosilver-containing antimicrobial material to the EVA molecular chain, reducing the migration rate of the nanosilver during processing or use, preventing localized loss of the antimicrobial component due to material deformation, and ensuring long-term antibacterial effects.
[0070] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as a preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any indirect modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.
Claims
1. An antibacterial and deodorizing insole material, characterized in that: The composition comprises the following components by weight: 82-100 parts of EVA, 11-15 parts of TPU, 4-6 parts of antibacterial material, 3-5 parts of dispersant and 2-3 parts of compatibilizer; The preparation of the antibacterial material comprises: Step 1: In an inert environment, ultrasonically mix anthranilic acid and anhydrous ethanol, add syringaldehyde, heat and mix, centrifuge to remove the solvent, wash, and freeze-dry to obtain a composite carrier; Step 2: Place the composite carrier in a silver nitrate solution and anhydrous ethanol and mix them evenly; add the sodium borohydride solution dropwise under vacuum stirring; continue stirring, filter, and rinse with water to obtain an antibacterial material.
2. The antibacterial and deodorizing insole material according to claim 1, characterized in that: The dispersant is polyvinylpyrrolidone.
3. The antibacterial and deodorizing insole material according to claim 1, characterized in that: The compatibilizer is EVA-g-GMA, wherein the GMA content is 1.5%.
4. The antibacterial and deodorizing insole material according to claim 1, characterized in that: The ultrasonic mixing is carried out at a power of 150-200W for 30-40 minutes; the heating mixing is carried out at a temperature of 50-60°C for 4-5 hours.
5. The antibacterial and deodorizing insole material according to claim 1, characterized in that: The mass ratio of the anthranilic acid, anhydrous ethanol and syringaldehyde is 12-15 g: 60-70 mL: 6.5-7.5 g.
6. The antibacterial and deodorizing insole material according to claim 1, characterized in that: The stirring time is continued for 1.0-1.5 hours; the mass ratio of the composite carrier, silver nitrate solution, anhydrous ethanol and sodium borohydride solution is 3-5 g: 6-9 mL: 300-400 mL: 30-38 mL.
7. The antibacterial and deodorizing insole material according to claim 1, characterized in that: The mass fraction of the silver nitrate solution is 1.5%; the mass fraction of the sodium borohydride solution is 5%.
8. A method for preparing the antibacterial and deodorizing insole material according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: adding EVA, TPU, antibacterial material, dispersant and compatibilizer into a twin-screw extruder, and performing extrusion granulation to obtain the antibacterial and deodorizing insole material.