Antibacterial material and preparation method and application thereof

Abstract

The present invention provides an antibacterial material and a preparation method and application thereof. The antibacterial material according to the present invention comprises glass microbeads, and a silver amine complex is attached to the surface of the glass microbeads. The antibacterial material of the present invention has a silver amine complex attached to the surface of the glass microbeads. When the antibacterial material is added to a polymer material, during the preparation and molding process of the polymer material, the silver amine complex is decomposed into nano silver particles by heat. The nano silver particles are attached to the surface of the glass microbeads, which can provide efficient bactericidal ability for the glass microbeads and the composite materials prepared with the nano silver particles as raw materials. The efficient antibacterial effect can be exerted without a large amount of addition, which reduces the cost and is conducive to large-scale popularization and application. The present invention also provides a preparation method and application of the antibacterial material.

Description

Technical Field

[0001] The invention belongs to the technical field of functional materials, and specifically relates to an antibacterial material and a preparation method and application thereof. Background Art

[0002] Diseases caused by bacterial infections have long been a threat to human health and safety. Nanosilver has been widely used in antibacterial products due to its high heat resistance, safety and broad-spectrum antibacterial properties. Plastic-related products are an important part of our daily lives, so it is also very important to improve the antibacterial properties of such products.

[0003] In the related art, the technical solution related to nanosilver antibacterial composite materials and their preparation is to add nanosilver particles to polymer resin. On the one hand, this method cannot guarantee the uniform distribution of nanosilver in the material; on the other hand, in order to make plastic products meet the antibacterial standards, a large amount of nanosilver particles needs to be added, which is costly and difficult to popularize and apply on a large scale.

[0004] Therefore, a new antibacterial material still needs to be developed. Summary of the invention

[0005] The present invention aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, the present invention provides an antibacterial material that can be evenly distributed in a polymer material, can exert antibacterial effects without a large amount of addition, is easy to prepare and has low cost, and is conducive to large-scale popularization and application.

[0006] The invention also provides a method for preparing the antibacterial material.

[0007] The invention also provides an antibacterial microbead.

[0008] The invention also provides a modified polymer material.

[0009] The invention also provides a household appliance.

[0010] A first aspect of the present invention provides an antibacterial material comprising glass microbeads, on the surface of which a silver amine complex is attached.

[0011] One of the technical solutions of the present invention regarding the antibacterial material has at least the following beneficial effects:

[0012] The antibacterial material of the present invention has a silver amine complex attached to the surface of glass microbeads. When the antibacterial material is added to a polymer material, the silver amine complex is decomposed into nano silver particles by heat during the preparation of the polymer material. The nano silver particles are attached to the surface of the glass microbeads and have a highly efficient bactericidal ability. When the antibacterial material of the present invention is used as a raw material to prepare a modified polymer material, a highly efficient antibacterial effect can be exerted without adding a large amount of antibacterial material, thereby reducing costs and facilitating large-scale popularization and application.

[0013] The antibacterial material of the present invention uses glass microspheres as a matrix and is easy to prepare. When used for polymer material modification, the polymer material can have lightweight and antibacterial characteristics, and has broad application prospects in industries such as home appliances and automobiles.

[0014] The antibacterial material of the present invention has a use cost significantly lower than that of nano silver particles.

[0015] The antibacterial material of the present invention has a silver amine complex attached to the surface of the glass microbeads. According to the difference of the silver precursor and the amine ligand used as the raw materials for preparing the silver amine complex, the decomposition temperature of the silver amine complex can be distributed between 90° C. and 150° C., which is well consistent with the processing and molding temperature of most polymer materials and has a wide range of applications.

[0016] According to some embodiments of the present invention, the particle size of the glass microbeads ranges from 10 μm to 80 μm.

[0017] According to some embodiments of the present invention, the glass microspheres are hollow glass microspheres, which are conducive to further achieving lightweight.

[0018] According to some embodiments of the present invention, raw materials for preparing the antibacterial material include glass microbeads, a silver precursor, an amine ligand, a silane coupling agent and a solvent.

[0019] The function of the silver precursor is to decompose and form nanosilver, which is attached to the surface of the glass beads.

[0020] The function of the amine ligand is to lower the decomposition temperature of the silver precursor and control the growth rate and particle size of nanosilver.

[0021] The function of the silane coupling agent is to modify the surface of the glass microspheres and increase the compatibility of the glass microspheres with the polymer resin.

[0022] The role of the solvent is to provide a reaction environment for the silver precursor, the amine ligand and the silane coupling agent, and to facilitate the full mixing and stirring of the raw materials.

[0023] According to some embodiments of the present invention, the mass ratio of the glass microbeads in the raw materials for preparing the antibacterial material is 5wt% to 15wt%.

[0024] According to some embodiments of the present invention, the molar ratio of the silver precursor to the amine groups in the amine ligand is 1:1-5.

[0025] According to some embodiments of the present invention, the molar ratio of the silver precursor to the amine groups in the amine ligand is 1:2-5.

[0026] According to some embodiments of the present invention, the molar ratio of the silver precursor to the amine groups in the amine ligand is 1:2.

[0027] According to some embodiments of the present invention, the silver precursor includes at least one of silver acetate, silver oxalate, silver citrate and silver lactate.

[0028] According to some embodiments of the present invention, the silver precursor is silver oxalate.

[0029] According to some embodiments of the present invention, the mass ratio of the silver precursor in the raw material for preparing the antibacterial material is 20wt% to 50wt%.

[0030] According to some embodiments of the present invention, the amine ligand includes at least one of 2-amino-2-methyl-1-propanol, diisobutylamine, propylenediamine, octylamine, quercetin and 3-ethylpyridine.

[0031] According to some embodiments of the invention, the amine ligand is 2-amino-2-methyl-1-propanol.

[0032] According to some embodiments of the present invention, the silane coupling agent includes at least one of 3-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane.

[0033] According to some embodiments of the present invention, the silane coupling agent includes at least one of KH-550, KH-540 and KH-551.

[0034] According to some embodiments of the present invention, the mass ratio of the silane coupling agent in the raw material for preparing the antibacterial material is 5wt% to 10wt%.

[0035] According to some embodiments of the invention, the solvent comprises at least one of water, ethanol, ethylene glycol, glycerol and tert-butyl alcohol.

[0036] According to some embodiments of the present invention, the solvent is deionized water.

[0037] According to some embodiments of the present invention, the mass ratio of the solvent in the raw material for preparing the antibacterial material is 25 wt % to 70 wt %.

[0038] The second aspect of the present invention provides a method for preparing the antibacterial material, the method comprising: mixing the raw materials for preparing the antibacterial material, heating and stirring, and then drying to obtain the antibacterial material.

[0039] A technical solution in the method for preparing an antibacterial material of the present invention has at least the following beneficial effects:

[0040] The method for preparing the antibacterial material of the present invention comprises mixing the raw materials for preparing the antibacterial material, that is, mixing the glass microbeads with the raw materials for preparing the silver amine complex, wherein the raw materials for preparing the silver amine complex specifically refer to a silver precursor, an amine ligand, a silane coupling agent and a solvent, and during heating and stirring, the raw materials for preparing the silver amine complex react to form the silver amine complex, which is attached to the surface of the glass microbeads, and then the solution is dried to obtain the antibacterial material. The preparation method is simple, does not require expensive equipment and harsh process conditions, has low manufacturing cost, and is easy to realize industrial production.

[0041] According to some embodiments of the present invention, the method further comprises pre-treating the glass microspheres.

[0042] According to some embodiments of the present invention, the pretreatment method may be to sequentially use acetone, acetic acid aqueous solution, and ethanol to ultrasonically clean the glass microbeads.

[0043] The role of pretreatment is to remove impurities and grease on the surface of glass beads, which is beneficial to the attachment of silver amine complex and nano silver particles.

[0044] According to some embodiments of the present invention, the temperature of the heating and stirring is 60°C to 90°C.

[0045] According to some embodiments of the present invention, the temperature of the heating and stirring is 80°C to 90°C.

[0046] According to some embodiments of the present invention, the heating and stirring time is 6 h to 12 h.

[0047] According to some embodiments of the present invention, the heating and stirring time is 8 h to 12 h.

[0048] According to some embodiments of the present invention, the heating and stirring speed is 200 rpm to 400 rpm.

[0049] The third aspect of the present invention provides an antibacterial micro-bead, which is formed by thermal decomposition of the antibacterial material.

[0050] A technical solution of the present invention regarding antibacterial microbeads has at least the following beneficial effects:

[0051] The antibacterial microbeads of the present invention are formed by thermal decomposition of the antibacterial material of the present invention and have all the beneficial effects of the antibacterial material, specifically:

[0052] The antibacterial microbeads of the present invention include glass microbeads and nanosilver particles attached to the surface of the glass microbeads, which can be evenly dispersed in polymer materials, provide excellent antibacterial effects for the polymer materials, do not require large amounts of addition, reduce costs, and are conducive to large-scale popularization and application.

[0053] The antibacterial microbeads of the present invention are formed by thermal decomposition of the antibacterial material of the present invention during the preparation or molding process of the polymer material. They are easy to prepare and can make the polymer material have antibacterial and lightweight characteristics. They have broad application prospects in the home appliance, automobile and other industries.

[0054] The fourth aspect of the present invention provides a modified polymer material, the raw materials for preparing the modified polymer material include the antibacterial material.

[0055] A technical solution of the present invention for modifying polymer materials has at least the following beneficial effects:

[0056] The modified polymer material of the present invention uses the antibacterial material of the present invention as a raw material for preparation, and thus has the beneficial effects of the antibacterial material. Specifically, the modified polymer material of the present invention contains the antibacterial material of the present invention in the raw material for preparation, and the surface of the glass microbeads of the antibacterial material has a silver amine complex. According to the difference between the silver precursor and the amine ligand, the decomposition temperature of the silver amine complex can be distributed between 90°C and 150°C, which is well matched with the processing and molding temperature of the polymer material. Therefore, during the processing and molding process of the polymer material, the silver amine complex is decomposed into nano silver particles by heat, and the nano silver particles are attached to the surface of the glass microbeads, which can provide efficient bactericidal ability for the glass microbeads and the composite material prepared with the nano silver particles as raw materials, and can exert efficient antibacterial effect without a large amount of addition, thereby reducing the cost and facilitating large-scale popularization and application.

[0057] The modified polymer material of the present invention is easy to prepare, can make the polymer material have the characteristics of light weight and antibacterial, and has broad application prospects in industries such as home appliances and automobiles.

[0058] According to some embodiments of the present invention, the modified polymer material includes modified plastic.

[0059] According to some embodiments of the present invention, the modified polymer material includes a polymer material matrix and antibacterial microbeads dispersed in the polymer material matrix, and the antibacterial microbeads are formed by thermal decomposition of the antibacterial material.

[0060] According to some embodiments of the present invention, in the modified polymer material, the added amount of the antibacterial material is 1 wt% to 10 wt%.

[0061] According to some embodiments of the present invention, the modified polymer material can be extruded into pellets in a twin-screw extruder and then injection molded by an injection molding machine.

[0062] The temperature of each zone of the twin-screw extruder can be: 180-210°C in zone 1, 200-230°C in zone 2, 200-220°C in zone 3, 220-220°C in zone 4, 190-220°C in zone 5, and the residence time is 1min to 3min.

[0063] A fifth aspect of the present invention provides a household appliance, the raw materials for preparing the household appliance include the antibacterial material.

[0064] One of the technical solutions of the present invention regarding household appliances has at least the following beneficial effects:

[0065] The household appliance of the present invention has all the beneficial effects of the antibacterial material of the present invention because the antibacterial material of the present invention is used. Specifically, in the household appliance of the present invention, antibacterial microbeads are dispersed in the preparation raw materials, and the antibacterial microbeads include a microbead matrix, and nanosilver particles are attached to the surface of the microbead matrix, which can provide efficient bactericidal ability for the modified polymer material. Compared with simple nanosilver particles, it can exert efficient antibacterial effect without adding a large amount, reducing the production cost, and further realizing the lightweight of the household appliance.

[0066] According to some embodiments of the present invention, the household appliance includes a refrigerator, a washing machine and an air conditioner. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] Figure 1 It is a schematic diagram of the thermal decomposition process of the antibacterial material of the present invention.

[0068] Reference numerals:

[0069] 1: Glass beads;

[0070] 2: Silver amine complex;

[0071] 3: Nanosilver particles. DETAILED DESCRIPTION

[0072] The following are specific embodiments of the present invention, and the technical solutions of the present invention are further described in conjunction with the embodiments, but the present invention is not limited to these embodiments.

[0073] In some embodiments of the present invention, the present invention provides an antibacterial material, including glass microbeads, and silver amine complexes are attached to the surfaces of the glass microbeads.

[0074] refer to Figure 1As shown, it can be understood that in the antibacterial material of the present invention, the silver amine complex 2 is attached to the surface of the glass microbead 1. When the antibacterial material is added to the polymer material, the silver amine complex 2 is decomposed into nano silver particles 3 by heat during the preparation of the polymer material. The nano silver particles 3 are attached to the surface of the glass microbead 1 and have efficient bactericidal ability. When the modified polymer material is prepared using the antibacterial material of the present invention as a raw material, a high efficient antibacterial effect can be exerted without adding a large amount of antibacterial material, which reduces the cost and is conducive to large-scale popularization and application.

[0075] It can also be understood that the antibacterial material of the present invention, which uses glass microspheres as a matrix, is easy to prepare. When used for polymer material modification, it can make the polymer material have the characteristics of lightweight and antibacterial, and has broad application prospects in the home appliance, automobile and other industries.

[0076] It can also be understood that the cost of using the antibacterial material of the present invention is significantly lower than simply adding nano-silver particles.

[0077] It can be understood that the antibacterial material of the present invention has a silver amine complex attached to the surface of the glass microbeads. Depending on the silver precursor and amine ligand used as the raw materials for preparing the silver amine complex, the decomposition temperature of the silver amine complex can be distributed between 90°C and 150°C, which is well consistent with the processing and molding temperature of most polymer materials and has a wide range of uses.

[0078] In some embodiments of the present invention, the particle size of the glass microspheres ranges from 10 μm to 80 μm.

[0079] In some embodiments of the present invention, the glass microspheres are hollow glass microspheres, which are beneficial for further achieving lightweight.

[0080] In some embodiments of the present invention, raw materials for preparing the antibacterial material include glass microbeads, a silver precursor, an amine ligand, a silane coupling agent and a solvent.

[0081] It should be noted that the role of the silver precursor is to decompose and form nanosilver, which is attached to the surface of the glass beads.

[0082] The function of the amine ligand is to lower the decomposition temperature of the silver precursor and control the growth rate and particle size of nanosilver.

[0083] The function of the silane coupling agent is to modify the surface of the glass microspheres and increase the compatibility of the glass microspheres with the polymer resin.

[0084] The role of the solvent is to provide a reaction environment for the silver precursor, the amine ligand and the silane coupling agent, and to facilitate the full mixing and stirring of the raw materials.

[0085] In some embodiments of the present invention, the mass ratio of glass microbeads in the raw materials for preparing the antibacterial material is 5wt% to 15wt%.

[0086] In some embodiments of the present invention, the molar ratio of the silver precursor to the amine groups in the amine ligand is 1:1-5.

[0087] In some embodiments of the present invention, the molar ratio of the silver precursor to the amine groups in the amine ligand is 1:2-5.

[0088] In some embodiments of the present invention, the molar ratio of the silver precursor to the amine groups in the amine ligand is 1:2.

[0089] In some embodiments of the present invention, the silver precursor includes at least one of silver acetate, silver oxalate, silver citrate, and silver lactate.

[0090] Silver acetate is a coordination compound, the actual structure is a dimer, in which silver is linearly coordinated. Silver acetate is a light-sensitive white crystalline solid that can be used as a water-soluble silver ion source. The CAS number of silver acetate is 563-63-3.

[0091] Silver oxalate decomposes into silver and carbon dioxide under geological conditions and is a precursor for producing nanosilver. The CAS number is 533-51-7.

[0092] The CAS number of silver citrate is 314040-92-1.

[0093] Silver lactate can be prepared by mixing equimolar amounts of silver nitrate solution and sodium lactate solution, and can be used as a disinfectant and preservative. The CAS number is 128-00-7.

[0094] In some embodiments of the present invention, the silver precursor is silver oxalate.

[0095] In some embodiments of the present invention, the mass ratio of the silver precursor in the raw material for preparing the antibacterial material is 20wt% to 50wt%.

[0096] In some embodiments of the present invention, the amine ligand includes at least one of 2-amino-2-methyl-1-propanol, diisobutylamine, propylenediamine, octylamine, quinamine and 3-ethylpyridine. Specifically:

[0097] The CAS number of 2-amino-2-methyl-1-propanol is 124-68-5.

[0098] The CAS number of diisobutylamine is 110-96-3.

[0099] The CAS number of propylenediamine is 78-90-0.

[0100] The CAS number of octylamine is 111-86-4.

[0101] The CAS number of amine is 2016-57-1.

[0102] The CAS number of 3-ethylpyridine is 536-78-7.

[0103] In some embodiments of the present invention, the amine ligand is 2-amino-2-methyl-1-propanol.

[0104] In some embodiments of the present invention, the silane coupling agent includes at least one of 3-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane.

[0105] In some embodiments of the present invention, the silane coupling agent includes at least one of KH-550, KH-540 and KH-551.

[0106] In some embodiments of the present invention, the mass ratio of the silane coupling agent in the raw materials for preparing the antibacterial material is 5wt% to 10wt%.

[0107] In some embodiments of the present invention, the solvent includes at least one of water, ethanol, ethylene glycol, glycerol and tert-butyl alcohol.

[0108] In some embodiments of the present invention, the solvent is deionized water.

[0109] In some embodiments of the present invention, the mass ratio of the solvent in the raw material for preparing the antibacterial material is 25wt% to 70wt%.

[0110] In some other embodiments of the present invention, a method for preparing an antibacterial material is provided, wherein the raw materials for preparing the antibacterial material are mixed, heated and stirred, and then dried to obtain the antibacterial material.

[0111] It can be understood that the preparation method of the antibacterial material of the present invention is to mix the raw materials for preparing the antibacterial material, that is, to mix the glass microspheres with the raw materials for preparing the silver amine complex. The raw materials for preparing the silver amine complex specifically refer to a silver precursor, an amine ligand, a silane coupling agent and a solvent. During the heating and stirring process, the raw materials for preparing the silver amine complex react to form a silver amine complex, which adheres to the surface of the glass microspheres. After that, the solution is dried to obtain the antibacterial material. The preparation method is simple, does not require expensive equipment and harsh process conditions, has a low manufacturing cost, and is easy to realize industrial production.

[0112] In some embodiments of the present invention, the preparation method further comprises pre-treating the glass microspheres.

[0113] In some embodiments of the present invention, the pretreatment method may be to use acetone, acetic acid aqueous solution, and ethanol to ultrasonically clean the glass microbeads in sequence.

[0114] The role of pretreatment is to remove impurities and grease on the surface of glass beads, which is beneficial to the attachment of silver amine complex and nano silver particles.

[0115] In some embodiments of the present invention, the temperature of heating and stirring is 60°C to 90°C.

[0116] In some embodiments of the present invention, the temperature of heating and stirring is 80°C to 90°C.

[0117] In some embodiments of the present invention, the heating and stirring time is 6 h to 12 h.

[0118] In some embodiments of the present invention, the heating and stirring time is 8 h to 12 h.

[0119] In some embodiments of the present invention, the speed of heating and stirring is 200 rpm to 400 rpm.

[0120] In some other embodiments of the present invention, an antibacterial microbead is provided. The antibacterial microbead is formed by thermal decomposition of the antibacterial material of the present invention.

[0121] It can be understood that the antibacterial microbeads of the present invention are formed by the thermal decomposition of the antibacterial material of the present invention, and have all the beneficial effects of the antibacterial material, specifically:

[0122] In addition, the antibacterial microbeads of the present invention, including glass microbeads and nanosilver particles attached to the surface of the glass microbeads, can be evenly dispersed in the polymer material, providing the polymer material with excellent antibacterial effect without the need for large-scale additions, thus reducing costs and facilitating large-scale popularization and application.

[0123] Furthermore, the antibacterial microbeads of the present invention can be formed by thermal decomposition of the antibacterial material of the present invention during the preparation or molding process of the polymer material. They are easy to prepare and can make the polymer material have antibacterial and lightweight characteristics. They have broad application prospects in the home appliance, automobile and other industries.

[0124] In some other embodiments of the present invention, a modified polymer material is provided, and the raw materials for preparing the modified polymer material include the antibacterial material of the present invention.

[0125] It can be understood that the modified polymer material of the present invention uses the antibacterial material of the present invention as the raw material for preparation, and thus has the beneficial effects of the antibacterial material, specifically:

[0126] The modified polymer material of the present invention comprises the antibacterial material of the present invention in the preparation raw material, the glass microbeads of the antibacterial material have silver amine complexes on their surfaces, and the decomposition temperature of the silver amine complexes can be distributed between 90°C and 150°C according to the difference between the silver precursor and the amine ligand, which is well matched with the processing and molding temperature of the polymer material. Therefore, in the processing and molding process of the polymer material, the silver amine complexes are decomposed into nano silver particles by heat, and the nano silver particles are attached to the surface of the glass microbeads, which can provide efficient sterilization ability for the glass microbeads and the composite material prepared by using the nano silver particles as raw materials, can exert efficient antibacterial effect without adding a large amount, reduce the cost, and facilitate large-scale popularization and application.

[0127] The modified polymer material of the present invention is easy to prepare, can make the polymer material have the characteristics of light weight and antibacterial, and has broad application prospects in industries such as home appliances and automobiles.

[0128] In some embodiments of the present invention, the modified polymer material includes modified plastic.

[0129] In some embodiments of the present invention, the modified polymer material includes a polymer matrix and antibacterial microbeads dispersed in the polymer matrix, and the antibacterial microbeads are formed by thermal decomposition of the antibacterial material of the present invention.

[0130] In some embodiments of the present invention, the amount of antibacterial material added to the modified polymer material is 1 wt% to 10 wt%.

[0131] In some embodiments of the present invention, the modified polymer material can be extruded into pellets in a twin-screw extruder and then injection molded by an injection molding machine.

[0132] The temperature of each zone of the twin-screw extruder can be: 180-210°C in zone 1, 200-230°C in zone 2, 200-220°C in zone 3, 220-220°C in zone 4, 190-220°C in zone 5, and the residence time is 1min to 3min.

[0133] In some other embodiments of the present invention, a household appliance is provided, wherein the raw materials for preparing the household appliance include the antibacterial material of the present invention.

[0134] It can be understood that the household appliance of the present invention, because it uses the antibacterial material of the present invention, has all the beneficial effects of the antibacterial material of the present invention. Specifically, in the household appliance of the present invention, antibacterial microbeads are dispersed in the preparation raw materials, and the antibacterial microbeads include a microbead matrix, and nanosilver particles are attached to the surface of the microbead matrix, which can provide efficient bactericidal ability for the modified polymer material. Compared with simple nanosilver particles, it can exert efficient antibacterial effect without adding a large amount, reducing the production cost, and at the same time, further realizing the lightweight of the household appliance.

[0135] In some embodiments of the present invention, the household appliances include a refrigerator, a washing machine, and an air conditioner.

[0136] The technical solution of the present invention will be better understood with reference to specific embodiments below.

[0137] It should be noted that in the following examples and comparative examples, the "parts" in the amounts of raw materials added are by mass unless otherwise specified.

[0138] Example 1

[0139] In this embodiment, an antibacterial material is first prepared. The antibacterial material includes glass microbeads, and silver amine complexes are attached to the surfaces of the glass microbeads.

[0140] The specific preparation method is:

[0141] The glass beads were ultrasonically cleaned for 5 min using acetone, 5% acetic acid aqueous solution, and ethanol in sequence to remove impurities on the surface of the glass beads.

[0142] Silver oxalate and 2-amino-2-methyl-1-propanol were stirred at room temperature in a molar ratio of 1:2 to obtain a silver organic source.

[0143] 10 parts of glass microbeads, 5 parts of silane coupling agent KH550, 15 parts of silver organic source and 70 parts of ethanol were taken, stirred at 8°C at a speed of 300 rpm for 8 hours, and then fully dried in an oven to obtain an antibacterial material.

[0144] The particle size of the glass beads is about 50 μm.

[0145] Furthermore, this embodiment prepares an antibacterial plastic. The specific preparation method is:

[0146] Take 5 parts of antibacterial material, 90 parts of polypropylene, and 5 parts of antioxidant 1010, extrude and granulate them in a twin-screw extruder, and then use an injection molding machine to injection mold them.

[0147] The temperature of each zone of the twin-screw extruder is: 180-210°C in zone 1, 200-230°C in zone 2, 200-220°C in zone 3, 220-220°C in zone 4, 190-220°C in zone 5, and the residence time is 2 min.

[0148] Example 2

[0149] In this embodiment, an antibacterial material is first prepared. The antibacterial material includes glass microbeads, and silver amine complexes are attached to the surfaces of the glass microbeads.

[0150] The specific preparation method is:

[0151] The glass beads were ultrasonically cleaned for 5 min using acetone, 5% acetic acid aqueous solution, and ethanol in sequence to remove impurities on the surface of the glass beads.

[0152] Silver oxalate and 2-amino-2-methyl-1-propanol were stirred at room temperature in a molar ratio of 1:2 to obtain a silver organic source.

[0153] 10 parts of glass microbeads, 5 parts of silane coupling agent KH550, 30 parts of silver organic source and 55 parts of ethanol were taken, stirred at 8°C at a speed of 300 rpm for 8 hours, and then fully dried in an oven to obtain an antibacterial material.

[0154] The particle size of the glass beads is about 50 μm.

[0155] Furthermore, this embodiment prepares an antibacterial plastic. The specific preparation method is:

[0156] Take 5 parts of antibacterial material, 90 parts of polypropylene, and 5 parts of antioxidant 1010, extrude and granulate them in a twin-screw extruder, and then use an injection molding machine to injection mold them.

[0157] The temperature of each zone of the twin-screw extruder is: 180-210°C in zone 1, 200-230°C in zone 2, 200-220°C in zone 3, 220-220°C in zone 4, 190-220°C in zone 5, and the residence time is 2 min.

[0158] Example 3

[0159] In this embodiment, an antibacterial material is first prepared. The antibacterial material includes glass microbeads, and silver amine complexes are attached to the surfaces of the glass microbeads.

[0160] The specific preparation method is:

[0161] The glass beads were ultrasonically cleaned for 5 min using acetone, 5% acetic acid aqueous solution, and ethanol in sequence to remove impurities on the surface of the glass beads.

[0162] Silver oxalate and 2-amino-2-methyl-1-propanol were stirred at room temperature in a molar ratio of 1:2 to obtain a silver organic source.

[0163] 10 parts of glass microbeads, 5 parts of silane coupling agent KH550, 15 parts of silver organic source and 70 parts of ethanol were taken, stirred at 8° C. at a speed of 300 rpm for 8 h, and then fully dried in an oven to obtain an antibacterial material.

[0164] The particle size of the glass beads is about 50 μm.

[0165] Furthermore, this embodiment prepares an antibacterial plastic. The specific preparation method is:

[0166] Take 5 parts of antibacterial material, 90 parts of polystyrene, and 5 parts of antioxidant 1010, extrude and granulate them in a twin-screw extruder, and then use an injection molding machine to injection mold them.

[0167] The temperature of each zone of the twin-screw extruder is: 180-210°C in zone 1, 200-230°C in zone 2, 200-220°C in zone 3, 220-220°C in zone 4, 190-220°C in zone 5, and the residence time is 2 min.

[0168] Example 4

[0169] In this embodiment, an antibacterial material is first prepared. The antibacterial material includes glass microbeads, and silver amine complexes are attached to the surfaces of the glass microbeads.

[0170] The specific preparation method is:

[0171] The glass beads were ultrasonically cleaned for 5 min using acetone, 5% acetic acid aqueous solution, and ethanol in sequence to remove impurities on the surface of the glass beads.

[0172] Silver oxalate and 2-amino-2-methyl-1-propanol were stirred at room temperature in a molar ratio of 1:2 to obtain a silver organic source.

[0173] 10 parts of glass microbeads, 5 parts of silane coupling agent KH550, 15 parts of silver organic source and 70 parts of ethanol were taken, stirred at 8° C. at a speed of 300 rpm for 8 h, and then fully dried in an oven to obtain an antibacterial material.

[0174] The particle size of the glass beads is about 50 μm.

[0175] Furthermore, this embodiment prepares an antibacterial plastic. The specific preparation method is:

[0176] Take 10 parts of antibacterial glass microbeads, 85 parts of polypropylene, and 5 parts of antioxidant 1010, extrude and granulate them in a twin-screw extruder, and then use an injection molding machine to perform injection molding.

[0177] The temperature of each zone of the twin-screw extruder is: 180-210°C in zone 1, 200-230°C in zone 2, 200-220°C in zone 3, 220-220°C in zone 4, 190-220°C in zone 5, and the residence time is 2 min.

[0178] Example 5

[0179] In this embodiment, an antibacterial material is first prepared. The antibacterial material includes glass microbeads, and silver amine complexes are attached to the surfaces of the glass microbeads.

[0180] The specific preparation method is:

[0181] The glass beads were ultrasonically cleaned for 5 min using acetone, 5% acetic acid aqueous solution, and ethanol in sequence to remove impurities on the surface of the glass beads.

[0182] Silver oxalate and octylamine were stirred at room temperature in a molar ratio of 1:2 to obtain a silver organic source.

[0183] 10 parts of glass microbeads, 5 parts of silane coupling agent KH550, 15 parts of silver organic source and 70 parts of ethanol were taken, stirred at 8° C. at a speed of 300 rpm for 8 h, and then fully dried in an oven to obtain an antibacterial material.

[0184] The particle size of the glass beads is about 50 μm.

[0185] Furthermore, this embodiment prepares an antibacterial plastic. The specific preparation method is:

[0186] Take 5 parts of antibacterial material, 90 parts of polypropylene, and 5 parts of antioxidant 1010, extrude and granulate them in a twin-screw extruder, and then use an injection molding machine to injection mold them.

[0187] The temperature of each zone of the twin-screw extruder is: 180-210°C in zone 1, 200-230°C in zone 2, 200-220°C in zone 3, 220-220°C in zone 4, 190-220°C in zone 5, and the residence time is 2 min.

[0188] Example 6

[0189] In this embodiment, an antibacterial material is first prepared. The antibacterial material includes glass microbeads, and silver amine complexes are attached to the surfaces of the glass microbeads.

[0190] The specific preparation method is:

[0191] Silver oxalate and 2-amino-2-methyl-1-propanol were stirred at room temperature in a molar ratio of 1:2 to obtain a silver organic source.

[0192] 10 parts of glass microbeads, 5 parts of silane coupling agent KH550, 15 parts of silver organic source and 70 parts of ethanol were taken, stirred at 8° C. at a speed of 300 rpm for 8 h, and then fully dried in an oven to obtain an antibacterial material.

[0193] The particle size of the glass beads is about 50 μm.

[0194] Furthermore, this embodiment prepares an antibacterial plastic. The specific preparation method is:

[0195] Take 5 parts of antibacterial material, 90 parts of polypropylene, and 5 parts of antioxidant 1010, extrude and granulate them in a twin-screw extruder, and then use an injection molding machine to injection mold them.

[0196] The temperature of each zone of the twin-screw extruder is: 180-210°C in zone 1, 200-230°C in zone 2, 200-220°C in zone 3, 220-220°C in zone 4, 190-220°C in zone 5, and the residence time is 2 min.

[0197] Comparative Example 1

[0198] In this comparative example, an antibacterial material is first prepared. The antibacterial material includes glass microbeads, and silver amine complexes are attached to the surfaces of the glass microbeads.

[0199] The specific preparation method is:

[0200] The glass beads were ultrasonically cleaned for 5 min using acetone, 5% acetic acid aqueous solution, and ethanol in sequence to remove impurities on the surface of the glass beads.

[0201] Silver oxalate and 2-amino-2-methyl-1-propanol were stirred at room temperature in a molar ratio of 1:2 to obtain a silver organic source.

[0202] 10 parts of glass microbeads, 15 parts of silver organic source and 70 parts of ethanol were taken, stirred at 8°C at a speed of 300 rpm for 8 hours, and then fully dried in an oven to obtain an antibacterial material.

[0203] The particle size of the glass beads is about 50 μm.

[0204] Furthermore, this embodiment prepares an antibacterial plastic containing nanosilver. The specific preparation method is:

[0205] Take 5 parts of antibacterial material, 90 parts of polypropylene, and 5 parts of antioxidant 1010, extrude and granulate them in a twin-screw extruder, and then use an injection molding machine to injection mold them.

[0206] The temperature of each zone of the twin-screw extruder is: 180-210°C in zone 1, 200-230°C in zone 2, 200-220°C in zone 3, 220-220°C in zone 4, 190-220°C in zone 5, and the residence time is 2 min.

[0207] Comparative Example 2

[0208] In this comparative example, an antibacterial material is first prepared. The antibacterial material includes glass microbeads, and silver amine complexes are attached to the surfaces of the glass microbeads.

[0209] The specific preparation method is:

[0210] The glass beads were ultrasonically cleaned for 5 min using acetone, 5% acetic acid aqueous solution, and ethanol in sequence to remove impurities on the surface of the glass beads.

[0211] The organic source of silver is silver oxalate.

[0212] 10 parts of glass microbeads, 5 parts of silane coupling agent KH550, 15 parts of silver organic source and 70 parts of ethanol were taken, stirred at 8° C. at a speed of 300 rpm for 8 h, and then fully dried in an oven to obtain an antibacterial material.

[0213] The particle size of the glass beads is about 50 μm.

[0214] Furthermore, this embodiment prepares an antibacterial plastic containing nanosilver. The specific preparation method is:

[0215] Take 5 parts of antibacterial material, 90 parts of polypropylene, and 5 parts of antioxidant 1010, extrude and granulate them in a twin-screw extruder, and then use an injection molding machine to injection mold them.

[0216] The temperature of each zone of the twin-screw extruder is: 180-210°C in zone 1, 200-230°C in zone 2, 200-220°C in zone 3, 220-220°C in zone 4, 190-220°C in zone 5, and the residence time is 2 min.

[0217] The antibacterial performance test in the present invention is carried out in accordance with the standard QB / T2591-2003 "Antibacterial Performance Test Method of Antibacterial Plastics". The antibacterial plastics prepared in the examples and comparative examples were tested, and the test results are shown in Table 1.

[0218] Table 1

[0219]

[0220]

[0221] According to the results in Table 1, after the glass microbeads were pretreated, the silver amine complex adhered more fully, the amount of nanosilver attached to the surface of the glass microbeads was greater, and the antibacterial performance was better.

[0222] Since the glass microbeads in Comparative Example 1 have not been surface-modified with a coupling agent, the interfacial compatibility between the glass microbeads and the resin is poor, resulting in insufficient dispersion of the glass microbeads in the product and reduced antibacterial performance.

[0223] In Comparative Example 2, compared with the silver amine complex, the silver precursor alone is difficult to adhere to the glass microspheres and difficult to be added to the resin along with the glass microspheres. At the same time, the decomposition of the silver precursor is uncontrolled, the nanosilver particles produced by the decomposition of the silver amine complex are smaller in size, and the antibacterial performance is reduced.

[0224] In some other embodiments of the present invention, the present invention provides a household appliance, and the raw materials for preparing the household appliance include the antibacterial material of the present invention.

[0225] It can be understood that the household appliances of the present invention, such as refrigerators, washing machines, and air conditioners, have good antibacterial effects as a whole or in specific parts, because the antibacterial materials of the present invention are used in the preparation of raw materials. For refrigerators, the growth of bacteria in the refrigerator can be inhibited, and the odor in the refrigerator can be reduced; for washing machines, the growth of bacteria and the adhesion of dirt in the washing machine can be inhibited; for air conditioners, it has a sterilization effect. The user experience of household appliances using the antibacterial materials of the present invention can be further improved.

[0226] The present invention has been described in detail above in conjunction with the embodiments, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge scope of ordinary technicians in the relevant technical field without departing from the purpose of the present invention.

Claims

1. An antibacterial material, characterized in that: The antibacterial material comprises glass microbeads, on the surface of which a silver amine complex is attached; the raw materials for preparing the antibacterial material comprise glass microbeads, a silver precursor, an amine ligand, a silane coupling agent and a solvent; The silver precursor includes at least one of silver acetate, silver oxalate, silver citrate and silver lactate; The amine ligand includes at least one of 2-amino-2-methyl-1-propanol, diisobutylamine, propylenediamine, octylamine, decylamine and 3-ethylpyridine; The silane coupling agent includes at least one of 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane; The solvent comprises at least one of water, ethanol, ethylene glycol, glycerol and tert-butyl alcohol; When the antibacterial material is added to a polymer material, during the preparation of the polymer material, the silver amine complex is decomposed into nano silver particles by heat, and the nano silver particles are attached to the surface of the glass micro beads and have bactericidal ability.

2. The antibacterial material according to claim 1, characterized in that: The particle size of the glass microbeads ranges from 10 μm to 80 μm.

3. The antibacterial material according to claim 1, characterized in that: The mass ratio of the glass microbeads in the raw materials for preparing the antibacterial material is 5wt% to 15wt%.

4. The antibacterial material according to claim 1, characterized in that: The molar ratio of the silver precursor to the amine group in the amine ligand is 1:1-5.

5. The antibacterial material according to claim 1, characterized in that: The mass ratio of the silver precursor in the raw material for preparing the antibacterial material is 20wt% to 50wt%.

6. The antibacterial material according to claim 1, characterized in that: The mass ratio of the silane coupling agent in the raw materials for preparing the antibacterial material is 5wt% to 10wt%.

7. The antibacterial material according to claim 1, characterized in that: The mass ratio of the solvent in the raw material for preparing the antibacterial material is 25wt% to 70wt%.

8. A method for preparing the antibacterial material according to any one of claims 1 to 7, characterized in that: The method comprises: mixing the raw materials for preparing the antibacterial material, heating and stirring, and then drying to obtain the antibacterial material.

9. The method according to claim 8, characterized in that The heating and stirring temperature is 60°C to 90°C.

10. The method according to claim 8, characterized in that The heating and stirring time is 6h to 12h.

11. The method according to claim 8, characterized in that The heating and stirring speed is 200 rpm to 400 rpm.

12. The method according to claim 8, characterized in that The method further comprises pre-treating the glass microspheres. 13.An antibacterial microbead, characterized in that: The antibacterial microbeads are formed by thermal decomposition of the antibacterial material according to any one of claims 1 to 7.

14. The antibacterial microbeads according to claim 13, characterized in that: The invention comprises glass micro beads and nano silver particles attached to the surface of the glass micro beads.

15. A modified polymer material, characterized in that: The preparation raw materials include the antibacterial material according to any one of claims 1 to 7.

16. The modified polymer material according to claim 15, characterized in that: The modified polymer material comprises a polymer material matrix and antibacterial microbeads dispersed in the polymer material matrix. The antibacterial microbeads are formed by thermal decomposition of the antibacterial material.

17. A household appliance, characterized in that: The preparation raw materials include the antibacterial material according to any one of claims 1 to 7.

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