A Highly Effective Antibacterial Particle and Its Preparation Method

Abstract

This application relates to the field of antibacterial particles, specifically disclosing a high-efficiency antibacterial particle and its preparation method. The antibacterial particle comprises the following raw materials in parts by weight: 10-50 parts of antibacterial masterbatch, 50-90 parts of carrier resin, 0.1-0.4 parts of antioxidant, and 1-2.2 parts of dispersant. The antibacterial masterbatch comprises a mixture of guanidine salt polymer and zinc salt in a mass ratio of (1-18):(82-99). The porosity of the antibacterial particle is 20-30%, and the pore size is 0.5-1 mm. The preparation method of the antibacterial particle includes the following steps: preparing the antibacterial masterbatch; preparing the antibacterial particle: compounding the antibacterial masterbatch with the carrier resin, adding antioxidant and dispersant, performing melt extrusion, water cooling, air drying, and pelletizing to obtain the antibacterial particle. The obtained antibacterial particle can rapidly release the effective components of guanidine salt and zinc ions, achieving rapid bactericidal effect, with excellent antibacterial effect, and can effectively solve the problem of moisture absorption of antibacterial agents in the air.

Description

Technical Field

[0001] This application relates to the field of antibacterial particles, and more specifically, to a highly efficient antibacterial particle and a method for preparing the same. Background Technology

[0002] With social development and progress, and the continuous improvement of living standards, people have increasingly higher requirements for their living and working environments, as well as for hygiene. Therefore, they also have higher demands for the various antibacterial materials on the market. Common antibacterial agents are divided into three categories: organic antibacterial agents, inorganic antibacterial agents, and natural antibacterial agents.

[0003] Polyguanidine salt antibacterial agents are a representative class of organic antibacterial agents. With an LD50 > 5000 mg / kg, they are practically non-toxic and extremely safe. These mainly include polyhexamethylene monoguanidine hydrochloride, polyhexamethylene biguanidine hydrochloride, and polyhexamethylene monoguanidine phosphate. This antibacterial agent is a new type of bactericide that has emerged in recent years, characterized by its broad spectrum, high efficiency, non-toxicity, non-irritation, and gentleness towards humans. Due to its good water solubility, it is widely used in the antibacterial treatment of water bodies and polymer materials.

[0004] Currently, antibacterial particles made from polyguanidine and resin materials are generally used in various fields. However, because polyguanidine materials are prone to absorbing moisture in the air and have poor stability, and cannot be well combined with resin materials, the antibacterial effect of the antibacterial particles is seriously affected. When antibacterial particles made from polyguanidine and resin materials are added to water, the release rate of the effective antibacterial components in the water is slow, and the bactericidal effect cannot be achieved quickly. Summary of the Invention

[0005] This application provides a highly efficient antibacterial particle and its preparation method, which can effectively solve the problem of moisture absorption of polyguanidine materials in the air. The obtained antibacterial particles do not absorb moisture or deteriorate even after being placed in the air for a long time, and the product has good stability. After being soaked in water, it can quickly release the effective components of guanidine salt and zinc ions, achieving rapid sterilization and excellent antibacterial effect.

[0006] Firstly, the highly efficient antibacterial granules provided in this application adopt the following technical solution:

[0007] A high-efficiency antibacterial granule, comprising the following raw materials in parts by weight: 10-50 parts of antibacterial masterbatch, 50-90 parts of carrier resin, 0.1-0.4 parts of antioxidant, and 1-2.2 parts of dispersant;

[0008] The antibacterial masterbatch comprises a mixture of guanidine salt polymer and zinc salt in a mass ratio of (1-18):(82-99);

[0009] The zinc salt mixture comprises 85-95 wt% soluble zinc salts and 5-15 wt% insoluble zinc-containing inorganic substances;

[0010] The antibacterial particles have a porosity of 20-30% and a pore size of 0.5-1 mm.

[0011] Experimental research has shown that mixing soluble zinc salts and insoluble zinc-containing inorganic substances in a certain proportion to form a zinc salt mixture, and then compounding it with a specific ratio of guanidine salt polymers and zinc salt mixtures to form an antibacterial masterbatch, can not only effectively solve the problem of polyguanidine materials easily absorbing moisture in the air, but also help solve the problems of bridging, particle agglomeration, and poor dispersibility during granulation. The resulting antibacterial granules will not absorb moisture or deteriorate even after being placed in the air for a long time, and the product has excellent stability. In addition to strictly controlling the dosage relationship between the components, it is also necessary to obtain antibacterial granules with specific porosity and pore size to achieve rapid release of guanidine salt active ingredients and zinc ions after soaking in water, thereby achieving rapid bactericidal effect and excellent antibacterial efficacy.

[0012] This application employs synergistic effects of soluble and insoluble zinc salts to solve the moisture absorption problem of polyguanidine materials while improving the bactericidal effect of the product, achieving a bactericidal rate of up to 99.99%. The resulting antibacterial particles can be used directly for sterilization treatment without the need for further compounding with other materials.

[0013] Preferably, the particle size of the zinc salt mixture is less than 20 μm.

[0014] Furthermore, the particle size of the zinc salt mixture can be 5μm, 10μm, 12μm, 15μm, 16μm, 18μm, etc.

[0015] Research experiments have shown that when the particle size of the zinc salt mixture is less than 20 μm, the antibacterial masterbatch has better dispersibility during granulation, and the resulting antibacterial particles can remain in the air for a longer time without absorbing moisture. The product is fine and there are no problems of bridging or particle agglomeration during granulation. This not only improves product stability but also helps to produce antibacterial particles with a higher concentration of effective antibacterial components.

[0016] Preferably, the soluble zinc salt is selected from one or more of zinc sulfate, zinc nitrate, and zinc chloride.

[0017] Furthermore, zinc sulfate is preferred as the soluble zinc salt. Soluble zinc salts can also be a combination of zinc nitrate and zinc chloride, or a combination of zinc sulfate and zinc chloride.

[0018] The insoluble zinc-containing inorganic material is selected from at least one of nano zinc oxide, zinc oxide whiskers, zinc sulfide, zinc carbonate, and zinc phosphate.

[0019] Furthermore, the insoluble zinc-containing inorganic material is preferably a combination of nano-zinc oxide and zinc oxide whiskers; the insoluble zinc-containing inorganic material can also be a combination of zinc sulfide and zinc carbonate, or a combination of zinc phosphate and nano-zinc oxide.

[0020] By adopting the above technical solution and optimizing the selection of soluble zinc salts and insoluble zinc-containing inorganic substances, not only can the problem of moisture absorption in air by antibacterial masterbatch be improved, and the stability and antibacterial effect of antibacterial particles be enhanced, but it can also be combined with other raw material components so that the antibacterial particles can quickly release the effective components of guanidine salts and zinc ions after being soaked in water, thereby achieving rapid sterilization.

[0021] Preferably, the carrier resin is a polyolefin resin.

[0022] Preferably, the melt index of the carrier resin is 20-40 g / 10 min.

[0023] As a further preferred option for the carrier resin, a polyolefin resin with a melt index of 30 g / 10 min is selected. For example, the polyolefin resin can be polyethylene resin, polypropylene resin, or polyisobutylene resin.

[0024] By adopting the above technical solution, selecting a suitable carrier resin and controlling the corresponding melt index, the processing performance of the carrier resin is guaranteed, and the antibacterial masterbatch is well loaded. During the granulation process, it can be quickly formed, which helps to improve the release rate of guanidine salt effective components and zinc ions, thereby achieving rapid sterilization.

[0025] Preferably, the guanidine salt polymer is at least one of polyhexamethylene monoguanidine hydrochloride, polyhexamethylene biguanidine hydrochloride, and polyhexamethylene monoguanidine phosphate.

[0026] Preferably, the dispersant is one of PP wax and PE wax.

[0027] Furthermore, antioxidants 1010 or 168 are preferred.

[0028] By employing the above technical solution, guanidine salt polymers, which are cationic polyelectrolytes with guanidine salt groups, can form electrostatic adsorption between the cations in their molecules and the anionic sites on the surface of bacterial cells, thus hindering the action of lysozyme, denaturing the cell surface structure, and destroying the cell membrane, thereby achieving a sterilization effect. Using guanidine salt polymers as one of the antibacterial masterbatches offers advantages such as low toxicity and non-irritation, endowing antibacterial particles with safe and highly effective sterilization.

[0029] Dispersants can further improve the lubrication and dispersion between raw material components, reduce component precipitation, aggregation or agglomeration, and promote uniform dispersion of the system. Antioxidants can effectively reduce the oxidation and discoloration of antibacterial particles. Dispersants and antioxidants work together to help improve the overall quality of antibacterial particles.

[0030] Secondly, this application provides a method for preparing antibacterial particles, using the following technical solution:

[0031] A method for preparing antibacterial granules includes the following steps:

[0032] Preparation of antibacterial masterbatch: The guanidine salt polymer and zinc salt mixture are blended evenly to obtain a composite antibacterial masterbatch;

[0033] Preparation of antibacterial granules: The antibacterial masterbatch is compounded with a carrier resin, and antioxidants and dispersants are added. The mixture is then melt-extruded, water-cooled, air-dried, and pelletized to obtain antibacterial granules.

[0034] Furthermore, the melt extrusion temperature is preferably 160-220℃.

[0035] Furthermore, during the melt extrusion process, the vacuum pump can be turned off to achieve the corresponding porosity and pore size of the particles during extrusion. Alternatively, other methods, such as adding a foaming agent, can be used to obtain antibacterial particles with the corresponding porosity and pore size; the foaming agent can be a commercially available product such as sodium carbonate, polyurethane foaming agent, or OBSH foaming agent.

[0036] By adopting the above technical solution, the antibacterial particles obtained above can quickly release the effective components of guanidine salt and zinc ions, achieve rapid sterilization, have excellent antibacterial effect, and can effectively solve the problem of moisture absorption of antibacterial agents in the air, resulting in a long storage time and good shelf life.

[0037] In summary, this application has the following beneficial effects: A zinc salt mixture is formed by mixing soluble zinc salts and insoluble zinc-containing inorganic substances in a certain proportion, and an antibacterial masterbatch is formed by compounding a guanidine salt polymer and the zinc salt mixture in a specific proportion. This not only effectively solves the problem of polyguanidine materials easily absorbing moisture in the air, but also helps to solve the problems of bridging, particle agglomeration, and poor dispersibility during granulation. The resulting antibacterial particles will not absorb moisture or deteriorate when placed in the air for a long time, exhibiting excellent product stability. Besides strictly controlling the dosage relationship between components, it is also necessary to obtain antibacterial particles with specific porosity and pore size to ensure that the antibacterial particles rapidly release the effective components of guanidine salts and zinc ions after immersion in water, achieving rapid bactericidal action and excellent antibacterial effect. Attached Figure Description

[0038] Figure 1 This is a schematic diagram of the product after the sample of Example 6 of this application has been placed in the air for 30 days.

[0039] Figure 2 This is a schematic diagram of the product of Comparative Example 1 of this application after being placed in the air for 5 minutes.

[0040] Figure 3 This is a schematic diagram of the product of Comparative Example 2 of this application after being placed in the air for 5 minutes. Detailed Implementation

[0041] The embodiments of the present invention will be described in detail below with reference to the examples. However, those skilled in the art will understand that the following examples are only for illustrating the present invention and should not be regarded as limiting the scope of the present invention. Specific conditions not specified in the examples shall be carried out according to conventional conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0042] Example

[0043] Example 1

[0044] The antibacterial granules comprise the following raw materials in parts by weight: 10 parts antibacterial masterbatch, 50 parts polyisobutylene resin with a melt index of 20 g / 10 min, 1 part PP wax, and 0.1 parts antioxidant 1010.

[0045] The antibacterial masterbatch consists of a mixture of polyhexamethylene monoguanidine hydrochloride and zinc salt in a mass ratio of 1:82;

[0046] The zinc salt mixture comprises 85 wt% zinc nitrate and 15 wt% nano zinc oxide; the particle size of the zinc salt mixture is less than 20 μm.

[0047] The preparation method of antibacterial granules includes the following steps:

[0048] Preparation of antibacterial masterbatch: Guanidine salt polymer and zinc salt mixture are blended evenly to obtain composite antibacterial agent component;

[0049] Preparation of antibacterial granules: Antibacterial masterbatch is compounded with carrier resin, antioxidant and dispersant are added and fed into a twin-screw extruder, and melt extrusion is carried out at a temperature of 160℃. The vacuum pump needs to be turned off during the melt extrusion process. After water cooling, air drying and pelletizing, antibacterial granules with a porosity of 20-22% and a pore size of 0.5-1mm are obtained.

[0050] Example 2

[0051] The antibacterial granules comprise the following raw materials in parts by weight: 50 parts antibacterial masterbatch, 90 parts polyethylene resin with a melt index of 40 g / 10 min, 2.2 parts PE wax, and 0.4 parts antioxidant 168.

[0052] The antibacterial masterbatch consists of a mixture of polyhexamethylene monoguanidine phosphate and zinc salt in a mass ratio of 18:99;

[0053] The zinc salt mixture comprises 95 wt% zinc chloride and 5 wt% zinc sulfide; the particle size of the zinc salt mixture is less than 20 μm.

[0054] Antibacterial granules include the following steps:

[0055] Preparation of antibacterial masterbatch: Guanidine salt polymer and zinc salt mixture are blended evenly to obtain composite antibacterial agent component;

[0056] Preparation of antibacterial granules: Antibacterial masterbatch is compounded with carrier resin, antioxidant and dispersant are added and fed into a twin-screw extruder, and melt extrusion is carried out at a temperature of 200℃. The vacuum pump needs to be turned off during the melt extrusion process. After water cooling, air drying and pelletizing, antibacterial granules with a porosity of 28-30% and a pore size of 0.5-1mm are obtained.

[0057] Example 3

[0058] The antibacterial granules comprise the following raw materials in parts by weight: 42 parts antibacterial masterbatch and 65 parts polypropylene resin with a melt index of 40 g / 10 min.

[0059] Two parts PE wax and 0.2 parts antioxidant 1010;

[0060] The antibacterial masterbatch consists of a mixture of polyhexamethylene monoguanidine hydrochloride and zinc salt in a mass ratio of 1:95;

[0061] The zinc salt mixture comprises 55 wt% zinc chloride, 30 wt% zinc sulfate, 10 wt% zinc carbonate, and 5 wt% zinc phosphate; the particle size of the zinc salt mixture is less than 20 μm.

[0062] Antibacterial granules include the following steps:

[0063] Preparation of antibacterial masterbatch: Guanidine salt polymer and zinc salt mixture are blended evenly to obtain composite antibacterial agent component;

[0064] Preparation of antibacterial granules: Antibacterial masterbatch is compounded with carrier resin, antioxidant and dispersant are added and fed into a twin-screw extruder, and melt extrusion is carried out at a temperature of 180℃. The vacuum pump needs to be turned off during the melt extrusion process. After water cooling, air drying and pelletizing, antibacterial granules with a porosity of 25-28% and a pore size of 0.5-1mm are obtained.

[0065] Example 4

[0066] The difference from Example 3 is that the antibacterial masterbatch includes a mixture of polyhexamethylene monoguanidine hydrochloride and zinc salt in a mass ratio of 15:84;

[0067] The zinc salt mixture comprises 70 wt% zinc chloride, 22 wt% zinc nitrate, 2 wt% zinc carbonate, 3 wt% zinc phosphate, and 3 wt% zinc oxide whiskers; the remainder is the same as in Example 3.

[0068] Example 5

[0069] The difference from Example 3 is that the antibacterial masterbatch includes a mixture of polyhexamethylene monoguanidine hydrochloride and zinc salt in a mass ratio of 13:90; all other aspects are the same as in Example 3.

[0070] Example 6

[0071] The difference from Example 5 is that the zinc salt mixture comprises 94 wt% zinc sulfate, 3 wt% nano zinc oxide, and 3 wt% zinc oxide whiskers; the rest are the same as in Example 5.

[0072] Example 7

[0073] The difference from Example 6 is that the particle size of the zinc salt mixture is 30-40 μm, while the rest is the same as in Example 6.

[0074] Comparative Example

[0075] Comparative Example 1

[0076] The difference from Example 6 is that the antibacterial masterbatch includes a mixture of polyhexamethylene monoguanidine hydrochloride and zinc salt in a mass ratio of 40:1; wherein the zinc salt mixture consists of 80 wt% zinc sulfate and 20 wt% nano zinc oxide, and the rest are the same as in Example 6.

[0077] Comparative Example 2

[0078] The difference from Example 6 is that the antibacterial masterbatch includes a mixture of polyhexamethylene monoguanidine hydrochloride and zinc salt in a mass ratio of 1:1, wherein the zinc salt mixture is a mixture of zinc sulfate and zinc nitrate in a mass ratio of 1:1; the rest is the same as in Example 6.

[0079] Comparative Example 3

[0080] The difference from Example 6 is that the zinc salt mixture is nano zinc oxide and zinc oxide whiskers in a mass ratio of 1:1, while the rest is the same as in Example 6.

[0081] Comparative Example 4

[0082] The difference from Example 6 is that the porosity of the antibacterial particles is 10% and the pore size is 1.5mm-2mm, while the rest are the same as in Example 6.

[0083] Comparative Example 5

[0084] The difference from Example 6 is that the porosity of the antibacterial particles is 35% and the pore size is 0.1-0.2 mm, while the rest are the same as in Example 6.

[0085] Performance testing

[0086] The antibacterial granules prepared in Examples 1-7 and Comparative Examples 1-5 were subjected to a hygroscopic test. The test method was as follows: 5g of each sample was weighed and placed on the same piece of paper, placed in the air, and the changes of each sample were observed after 5 minutes and 30 days. The results are recorded in Table 1.

[0087] Table 1

[0088]

[0089]

[0090] As can be seen from Examples 1-7 and Table 1, the antibacterial particles obtained in this application do not absorb moisture or deteriorate even after being exposed to air for a long time, demonstrating excellent product stability. Furthermore, through Example 6 and Comparative Example 1, combined with… Figure 1-3 As can be seen, the sample prepared in Example 6 remained dry and fine after 30 days, while the antibacterial granules prepared in Comparative Example 1 severely absorbed moisture and could not be used normally. Similarly, the antibacterial granules prepared in Comparative Example 2 also showed obvious particle aggregation and clumping, with significant moisture absorption. Therefore, the ratio of the amounts of guanidine salt mixture and zinc salt polymer, as well as the composition of the zinc salt mixture, has a significant impact on the moisture absorption performance of the obtained antibacterial granules. Only components and ratios within the scope of this application can effectively improve the stability of the antibacterial granules, ensuring that the product will not absorb moisture or deteriorate even after prolonged exposure to air.

[0091] Take 1g of the samples prepared in Examples 1-7 and Comparative Examples 1-5 and add them to 100mL of tap water. Soak for 2 hours. Use infrared spectroscopy to qualitatively detect whether guanidine salts in the solution have dissolved. Use spectrophotometry to measure the zinc ion content in the solution. Record the results in Table 2.

[0092] Table 2

[0093] Guanidine salts Zinc ion content / mg Example 1 exist 182 Example 2 exist 178 Example 3 exist 189 Example 4 exist 185 Example 5 exist 192 Example 6 exist 197 Example 7 exist 190 Comparative Example 1 exist 77 Comparative Example 2 exist 90 Comparative Example 3 exist / Comparative Example 4 exist 98 Comparative Example 5 exist 106

[0094] As can be seen from Examples 1-7 and Table 2, the obtained antibacterial particles, after being soaked in water, rapidly release guanidine salts and zinc ions within a very short soaking time, and the zinc ion content is high, achieving a rapid bactericidal effect. From Examples 6 and Comparative Examples 1-3, combined with Table 2, it can be seen that in Comparative Examples 1-3, adjusting the dosage relationship between the guanidine salt mixture and the zinc salt polymer, as well as the composition of the zinc salt mixture, significantly affected the release of both the effective component of guanidine salts and zinc ions. In Comparative Example 3, because insoluble zinc-containing inorganic substances were used, the zinc ion content could not be detected. In Comparative Examples 4-5, due to the poor porosity and pore diameter of the antibacterial particles, even if the effective component of guanidine salts could be detected, the release of zinc ions was significantly reduced, severely affecting the bactericidal effect.

[0095] Therefore, it can be seen that the raw material components of this application complement each other and work synergistically to improve the stability of the antibacterial particles, so that the product will not absorb moisture and deteriorate even when placed in the air for a long time. At the same time, after being soaked in water for a short time, it can quickly release the guanidine salt effective ingredients and high content of zinc ions to achieve rapid sterilization.

[0096] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A high efficiency antibacterial particle, characterized in that, The antibacterial granule comprises the following raw materials by weight: 10-50 parts of antibacterial masterbatch, 50-90 parts of carrier resin, 0.1-0.4 parts of antioxidant, and 1-2.2 parts of dispersant; The antibacterial masterbatch comprises a mixture of guanidinium salt polymer and zinc salt in a mass ratio of (1-18):(82-99); the guanidinium salt polymer is at least one of polyhexamethylene monoguanidinium hydrochloride, polyhexamethylene biguanidinium hydrochloride, and polyhexamethylene monoguanidinium phosphate; The zinc salt mixture comprises 85-95 wt% of soluble zinc salt and 5-15 wt% of insoluble zinc-containing inorganic substance; the soluble zinc salt is selected from one or more of zinc sulfate, zinc nitrate, and zinc chloride; the insoluble zinc-containing inorganic substance is selected from at least one of nano-zinc oxide, zinc oxide whisker, zinc sulfide, zinc carbonate, and zinc phosphate; The antibacterial granule has a porosity of 20-30% and a pore size of 0.5-1 mm.

2. The high efficiency antibacterial particle according to claim 1, wherein: The particle size of the zinc salt mixture is less than 20 μm.

3. The high efficiency antibacterial particle of claim 1, wherein: The carrier resin is polyolefin resin.

4. The high efficiency antibacterial particle of claim 3, wherein: The carrier resin has a melt index of 20-40 g / 10 min.

5. The high efficiency antimicrobial particle of claim 1, wherein: The dispersant is one of PP wax and PE wax.

6. Process for the preparation of the highly efficient antibacterial particles according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: Preparation of antibacterial masterbatch: uniformly blending the guanidinium salt polymer and the zinc salt mixture to obtain a composite antibacterial agent component; Preparation of antibacterial granule: compounding the antibacterial masterbatch with the carrier resin, adding the antioxidant and the dispersant, and then performing melt extrusion, water cooling, air drying, and granulation to obtain the antibacterial granule.

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