CN111892301B - Glass antibacterial micro-beads and glass antibacterial resin - Google Patents
Glass antibacterial micro-beads and glass antibacterial resin Download PDFInfo
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- CN111892301B CN111892301B CN202010810254.5A CN202010810254A CN111892301B CN 111892301 B CN111892301 B CN 111892301B CN 202010810254 A CN202010810254 A CN 202010810254A CN 111892301 B CN111892301 B CN 111892301B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—Glass
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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Abstract
The invention discloses a glass antibacterial bead and glass antibacterial resin. The glass antibacterial micro-bead comprises the following components in molar content: b2O3：35～55mol％；SiO2: 15-40 mol%; alkali metal oxide(s): 2-25 mol%; ZnO: 5-30 mol%; antibacterial oxides: 0.02-5 mol% of antibacterial oxide Ag2O and/or CuO; the mol% is the percentage of each component in the total molar weight of the glass antibacterial micro-beads; the glass antibacterial micro-beads are prepared by a flame floating method; in the flame floating method, the temperature of the flame is 920-990 ℃. The glass antibacterial microspheres have excellent heat resistance and antibacterial property, and can keep the surface of a product smooth and flat, and have uniform particle size distribution and good uniformity when being applied to preparation of glass antibacterial resin.
Description
Technical Field
The invention relates to glass antibacterial microspheres and glass antibacterial resin.
Background
In recent years, with the development of science and technology, the living standard of people is increasing, and more people begin to look at environmental sanitation. In life, problems due to the growth of bacteria are frequently encountered, and therefore, antibacterial products are urgently needed. The antibacterial agent is used as a key component of antibacterial products and mainly comprises inorganic and organic antibacterial agents. Because the inorganic antibacterial agent has higher heat resistance and is more stable in the processing process, the market share of the inorganic antibacterial agent is continuously improved.
The commonly used inorganic antibacterial agent is a composition prepared by mixing silver, zinc and a composition thereof as antibacterial ingredients and an inorganic material as a carrier, and comprises zeolite, zirconium phosphate, glass and the like. Because the inorganic antibacterial glass has safe, stable and controllable performance, the inorganic antibacterial glass is widely applied to resin products.
At present, plastic products are widely applied, however, in the fields of electronics, aviation, aerospace, instruments and meters and the like, the surface roughness of the plastic is highly required. The glass antibacterial product is prepared by processing glass with antibacterial components obtained by melting into powder by adopting a ball milling or airflow crushing method, screening the powder and testing the particle size of the powder by a laser particle sizer. For example, in the extrusion process, the powder blocks the filter screen, so that the actual content of the antibacterial component in the product is reduced, and the filtering pressure of equipment is increased, so that the process is unstable. In other applications, such as coating or weaving, although the range of particle size indicated by a laser particle size analyzer meets the application requirements, the deviation of the result from the actual particle size and distribution is large due to the testing mechanism, and many process adverse factors or product surface roughness and other problems occur in the application process. Based on the above problems, the application range of the glass antibacterial product is limited.
Disclosure of Invention
The invention aims to solve the technical problems of uneven particle size distribution, larger surface roughness and poorer antibacterial performance of glass antibacterial powder in the prior art and the defect that more antibacterial oxides need to be added, and provides the glass antibacterial microspheres and the glass antibacterial resin. The glass antibacterial microspheres have excellent heat resistance and antibacterial property, and can keep the surface of a product smooth and flat, the particle size distribution is uniform and the uniformity of a final product is good when the glass antibacterial microspheres are applied to preparation of glass antibacterial resin.
The invention solves the technical problems through the following technical scheme.
The invention provides a glass antibacterial bead which comprises the following components in molar content:
B2O3：35～55mol％；
SiO2：15～40mol％；
alkali metal oxide(s): 2-25 mol%;
ZnO：5～30mol％；
antibacterial oxides: 0.02-5 mol%, the antibacterial oxide is Ag2O and/or CuO; the Ag is2The content of O is 0 to 0.3 mol% but not 0; the content of the CuO is 0-5 mol% but not 0; the mol% is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads;
the glass antibacterial micro-beads are prepared by a flame floating method;
in the flame floating method, the temperature of flame is 920-990 ℃.
In the present invention, said B2O3The content of (B) is preferably 40 to 51mol%, for example 40mol%, 45mol% or 51 mol%.
In the present invention, the SiO is2The content of (b) is preferably 20 to 35mol%, for example 20mol%, 25mol%, 30mol% or 35 mol%. SiO in the invention2Less than 15mol% is not favorable for forming glass state, ceramics is easy to appear in the melting process, and if more than 55 mol%, the melting temperature is increased, and the antibacterial performance is not easy to appear.
In the present invention, the content of the alkali metal oxide is preferably 5 to 15mol%, for example, 5mol%, 5.3mol%, 11mol% or 15 mol%. In the present invention, if the alkali metal oxide is less than 2mol%, it will cause difficulty in melting, and if it is more than 25mol%, it will reduce the antibacterial property of the glass antibacterial beads.
In the present invention, the alkali metal oxide may be an alkali metal oxide conventionally used in the art for preparing glass antibacterial products. The alkali metal oxide may be Na2O and/or K2O。
When the alkali metal oxide contains Na2When O is, the Na is2The content of O is preferably 3.3 to 15mol%, such as 3.3mol%, 5mol%, 11mol% or 15mol%, where mol% is the percentage of the total molar amount of the glass antimicrobial micro-beads.
When said alkali metal oxide contains K2When O is, the K is2The content of O is preferably 1 to 3mol%, for example 2mol%, and the mol% is the percentage of the total molar amount of the glass antibacterial micro-beads.
In the present invention, the content of ZnO is preferably 8 to 20mol%, for example 8mol%, 15mol% or 20 mol%. In the invention, the content of ZnO is less than 5mol%, the antibacterial property of the glass is not easy to embody, and the content of ZnO is more than 30mol%, the glass melting temperature is increased.
In the present invention, the content of the antibacterial oxide is preferably 0.03 to 4.0mol%, for example, 0.03mol%, 0.7 mol%, 3mol% or 4 mol%.
In the present invention, the Ag is2The content of O is preferably 0.02 to 0.03mol%, for example 0.02mol% or 0.03 mol%. When the antibacterial oxide of the invention is Ag2When O is used, the content of less than 0.02-0.03 mol% is only required to be added, so that the better antibacterial property can be achieved, and the cost for preparing the glass antibacterial microspheres is reduced.
In the present invention, the content of CuO is preferably 0.68 to 4.0mol%, for example, 0.68mol%, 3mol% or 4 mol%.
In the present invention, the glass antibacterial micro-beads may further include an alkaline earth metal oxide.
The content of the alkaline earth metal oxide may be conventional in the art, and is preferably 0 to 15mol% but not 0, and more preferably 2 to 4mol%, for example, 2mol%, 3.97mol% or 4mol%, where mol% is the percentage of the total molar amount of the glass antimicrobial micro beads.
The kind of the alkaline earth metal oxide may be a kind of an alkaline earth metal oxide that is conventional in the art. The alkaline earth metal oxide is typically MgO and/or CaO in kind.
When the glass antibacterial beads contain MgO, the content of MgO is preferably 1 to 4mol%, for example, 1mol% or 3.97mol%, where mol% is the percentage of the total molar amount of the glass antibacterial beads.
When the glass antibacterial micro beads contain CaO, the content of CaO is preferably 2 to 3mol%, for example, 2mol% or 3mol%, where mol% is the percentage of the total molar amount of the glass antibacterial micro beads.
In the invention, the glass antibacterial micro-beads can also comprise P2O5、Al2O3、Y2O3And CeO2One or more of (B), e.g. Al2O3。
Wherein, when the glass antibacterial micro-beads contain Al2O3When being made of Al2O3The content of (b) is preferably 1 to 3mol%, for example 2mol%, and the mol% is a percentage of the total molar amount of the glass antibacterial micro-beads.
In a preferred embodiment of the present invention, the glass antibacterial micro-beads are composed of the following components by mole: b2O3：40mol％、SiO2：25mol％、MgO：3.97mol％、Na2O：11mol％、ZnO：20mol％、Ag2O: 0.03mol percent, wherein the mol percent is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads.
In a preferred embodiment of the present invention, the glass antibacterial micro-beads are composed of the following components by mole: b is2O3：45mol％、SiO2：20mol％、CaO：2mol％、Na2O: 15mol%, ZnO: 15mol%, CuO: 3mol percent, and the mol percent is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads.
In a preferred embodiment of the present invention, the glass antimicrobial micro-beads are composed of the following components by mole: b2O3：51mol％、SiO2：35mol％、Na2O：3.3mol％、K2O：2mol％、ZnO：8mol％、Ag2O: 0.02mol%, CuO: 0.68mol%, and the mol% is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads.
In a certain aspect of the inventionIn a preferred embodiment, the glass antibacterial micro-beads comprise the following components in molar content: b is2O3：40mol％、SiO2：30mol％、MgO：1mol％、CaO：3mol％、Na2O：5mol％、ZnO：15mol％、CuO：4mol％、Al2O3: 2mol percent, and the mol percent is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads.
In the present invention, the temperature of the flame is preferably 950 to 970 ℃, for example 950 ℃.
In the flame floating method, the particle state of the glass antibacterial micro-beads is laminar flow movement; the laminar motion may be in the sense conventionally understood by those skilled in the art, and generally refers to the laminar flow of a fluid. In the flame floating method, when the movement mode of the particles of the glass antibacterial micro-beads in the furnace is laminar flow movement, the Reynolds number of the particles is usually less than 1.
In the present invention, it is known to those skilled in the art that the particles of the glass antibacterial beads are generally preheated before the flame floating method.
Wherein the temperature of said preheating may be conventional in the art, e.g. 400 ℃.
Wherein the preheating typically further comprises preheating natural gas and combustion supporting gas to produce the flame.
In the present invention, the time for the flame floating method of the particles of the glass antibacterial microbeads may be conventional in the art, and is preferably 20 to 40 min. The time generally refers to the time during which the temperature of the flame is maintained.
In the present invention, it is known to those skilled in the art that the flame floating method is generally followed by a cooling operation. The cooling is usually referred to as rapid cooling. Wherein, the cooling generally means cooling to below 300 ℃.
Wherein said cooling is generally followed by a sieving operation. And the screen during screening is selected according to the particle size of the glass antibacterial micro-beads before the flame floating method is carried out. The mesh number of the screen is, for example, 100 mesh or 200 mesh.
In the present invention, the preparation method of the particles of the glass antibacterial micro-beads may be a preparation method of a glass antibacterial product that is conventional in the art. Preferably comprising the steps of: the glass antibacterial microspheres are prepared by mixing the raw materials according to the components, and then melting, cooling, drying and pulverizing the mixture to obtain the glass antibacterial microspheres.
Wherein, the sources of the raw materials in the glass antibacterial micro-beads can be conventional sources in the field.
B is2O3Can include B2O3And/or H3BO3。
The SiO2Can include SiO2And/or silica sand.
When the alkali metal oxide contains Na2When it is O, the Na is2The source of O may include Na2CO3And NaHCO3One or more of (a).
When the alkali metal oxide contains K2When O is, the K is2Sources of O may include K2CO3And/or KHCO3。
The Ag is2The source of O may include Ag2O and/or AgNO3。
The source of ZnO may comprise ZnO.
The source of CuO may include CuO and/or Cu (OH)2。
When the glass antimicrobial beads comprise MgO, the source of MgO may comprise MgO and/or MgCO3。
When the glass antibacterial micro-beads contain CaO, the source of the CaO can be CaO or CaCO3。
Wherein the melting temperature can be 1100-1350 ℃, such as 1200 ℃.
Wherein the melting time can be 20-120 min.
Wherein, the cooling can be carried out by cold water. The temperature of the cold water is generally room temperature. In the invention, the room temperature is generally 10-30 ℃.
Wherein the drying temperature can be 50-110 ℃. The drying time may be 2 to 12 hours, for example 6 hours.
Wherein, the powder preparation can adopt a mode of airflow crushing and/or ball milling and sieving. The milling preferably comprises the steps of: and carrying out ball milling on the crude glass obtained after drying by adopting a ball mill, and then sieving.
In the invention, before the flame floating method is carried out, the particle diameter of D10 of the glass antibacterial bead particles can be 2.5-3 microns, such as 2.7 microns, 2.8 microns or 2.9 microns; the particle size of D50 of the particles of the glass antibacterial micro-beads can be 10-10.5 microns, such as 10.1 microns, 10.2 microns or 10.3 microns; the particle size of D99 of the particles of the glass antimicrobial beads may be 59 to 61 micrometers, such as 59.4 micrometers, 59.6 micrometers, 60.3 micrometers, or 61 micrometers.
The invention also provides glass antibacterial resin which comprises the glass antibacterial micro-beads and a resin material.
In the present invention, the mass ratio of the glass antibacterial beads to the resin material may be a mass ratio that is conventional in the art, for example (0.4 to 1.5): (98.5 to 99.6), for example, 1: 99.
in the present invention, the kind of the resin material may be a resin material that is conventional in the art, for example, a polypropylene resin, a thermoplastic polyurethane, or an ABS resin. Wherein the polypropylene resin is, for example, M800E; the ABS resin is, for example, PA-758 or PA-757K.
In the present invention, the surface roughness of the glass antibacterial resin may be 0.7 to 1 μm, for example, 0.8 μm. The surface roughness refers to the arithmetic mean of the roughness profile of the glass antibacterial resin prepared into a plate-shaped structure.
In the present invention, the preparation method of the glass antibacterial resin may be a preparation method that is conventional in the art. The preparation method of the antibacterial resin preferably comprises the following steps: and mixing the glass antibacterial microspheres with the resin material, and then granulating and injection molding to obtain the antibacterial glass microsphere.
Wherein, the mixing can be a conventional mixing mode in the field, and the glass antibacterial micro-beads and the resin material are uniformly mixed.
Wherein, the granulating process can be a conventional granulating process in the field. The granulation is typically extrusion granulation. The temperature of the extrusion granulation is preferably 195-205 ℃, such as 200 ℃.
Wherein, the injection molding process can be the conventional injection molding in the field. The injection molding temperature is preferably 210-230 ℃, such as 220 ℃.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: according to the invention, through the matching of all components in the particles of the glass antibacterial microspheres, the antibacterial performance of the particles of the glass antibacterial microspheres is excellent, and the glass antibacterial microspheres with better and uniform particle size distribution are prepared by combining a specific flame floating method. The D10 particle size distribution of the glass antibacterial beads is 3.8-4.5 microns, the D50 particle size distribution is 10-10.5 microns, the D99 particle size distribution is 32-33.5 microns, and the particle size distribution is uniform. When the glass antibacterial microspheres are mixed with a resin material to prepare the antibacterial resin, the antibacterial property is further improved, and the resin product has a smooth and flat surface and low roughness. Compared with the antibacterial effect of the product prepared from the particles of the glass antibacterial microspheres which are not subjected to the specific flame floating method and the resin material, the antibacterial effect of the antibacterial resin prepared from the antibacterial microspheres is improved by 7-19%. The final resin product has better antibacterial effect on escherichia coli and staphylococcus aureus, and the antibacterial performance value can reach 3CFU/cm2Above, up to 5.9CFU/cm2。
Drawings
Fig. 1 is a schematic view of the glass antibacterial beads and particles thereof in example 1, wherein fig. 1a is a schematic view of the particles of the glass antibacterial beads, and fig. 1b is a schematic view of the glass antibacterial beads.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The polypropylene resin PP in the following examples and comparative examples was derived from: the product is produced by China petrochemical Shanghai petrochemical industry Co., Ltd, and the model number is as follows: M800E.
Example 1
(1) Glass antibacterial micro-bead
The raw materials were prepared according to the formulation of example 1 in table 1 below. The specific implementation method comprises the following steps: weighing H which is converted into corresponding amount according to the proportion3BO3、SiO2、MgO、Na2CO3、ZnO、AgNO3The raw materials are evenly mixed and then placed in a corundum crucible, the corundum crucible is kept warm for 120 minutes in a high-temperature furnace at 1200 ℃ to be melted into liquid, and then the liquid is discharged and placed in cold water to be cooled in the water. Taking out the glass, spreading the glass on a tray, and placing the tray in a 110 ℃ oven for heat preservation for 6 hours to obtain the crude glass. And then ball-milling by using a zirconium dioxide ball mill, and screening by using a 100-mesh screen to obtain the particles of the glass antibacterial micro-beads.
And (4) after the treatment by a flame floating method, screening to obtain the glass antibacterial micro-beads. The specific operation of the flame floating method is as follows: preheating the particles of the glass antibacterial microspheres to 400 ℃, putting the particles into an adult plant furnace to perform laminar flow motion, keeping the flame temperature at 950 ℃ in the flame for 20min, cooling the product to below 300 ℃ by a rapid cooling device after the particles of the glass antibacterial microspheres are melted, and passing the product through a 100-mesh screen after the particles are recovered to obtain the glass antibacterial microspheres.
(2) Glass antibacterial resin
Adding 1.0% of the addition amount of the particles of the glass antibacterial beads and the glass antibacterial beads into polypropylene resin (PP), extruding and granulating at 200 ℃, and then performing injection molding at 220 ℃ to obtain an antibacterial PP-1 plate and an antibacterial PP-2 plate respectively.
Example 2
The raw materials are prepared according to the formula of example 2 in table 1, and the raw material sources of the components are respectively as follows: h3BO3、SiO2、CaO、Na2CO3、ZnO、Cu(OH)2. The preparation methods of the glass antibacterial beads and the glass antibacterial resin are the same as example 1.
Example 3
The raw materials are prepared according to the formula of example 3 in table 1, and the raw material sources of the components are respectively as follows: h3BO3、SiO2、Na2CO3、K2CO3、ZnO、AgNO3、Cu(OH)2. The preparation methods of the glass antibacterial beads and the glass antibacterial resin are the same as example 1.
Example 4
The raw materials were prepared according to the formulation of example 4 in table 1, and the raw material sources of the components were as follows: h3BO3、SiO2、Na2CO3、K2CO3、ZnO、AgNO3、Cu(OH)2. The preparation methods of the glass antibacterial beads and the glass antibacterial resin are the same as example 1.
Comparative example 1
The raw materials are prepared according to the formula of the comparative example 1 in the table 1, and the raw material sources of the components are respectively as follows: h3BO3、SiO2、Na2CO3、ZnO、Cu(OH)2. The preparation methods of the glass antibacterial beads and the antibacterial resin are the same as example 1.
Comparative example 2
The particles of the glass antibacterial microspheres prepared in the example 1 in the table 1 are treated by a flame floating method and are screened to obtain the glass antibacterial microspheres. The specific operation of the flame floating method is as follows: preheating the glass antibacterial agent to 400 ℃, putting the glass antibacterial agent into a bead forming furnace, keeping the flame temperature at 800 ℃ for 20min, melting the particles of the glass antibacterial beads, cooling the product to below 300 ℃ by a rapid cooling device, recycling, and screening by a 100-mesh screen to obtain the glass antibacterial beads.
The components and contents of the glass antibacterial micro beads of examples 1 to 4 and comparative examples 1 and 2 are shown in table 1 below.
TABLE 1 (unit: mol%)
| B2O3 | SiO2 | MgO | CaO | Na2O | K2O | ZnO | Ag2O | CuO | Al2O3 | |
| Example 1 | 40 | 25 | 3.97 | / | 11 | / | 20 | 0.03 | / | / |
| Example 2 | 45 | 20 | / | 2 | 15 | / | 15 | / | 3 | / |
| Example 3 | 51 | 35 | / | / | 3.3 | 2 | 8 | 0.02 | 0.68 | / |
| Example 4 | 40 | 30 | 1 | 3 | 5 | 15 | 4 | 2 | ||
| Comparative example 1 | 35 | 45 | / | / | 5 | / | 12 | / | 3 | / |
| Comparative example 2 | 40 | 25 | 3.97 | / | 11 | / | 20 | 0.03 | / | / |
Effect example 1
1. And (3) testing the particle size, namely testing the particle size of the glass antibacterial micro-beads and the particles of the glass antibacterial micro-beads prepared in the examples 1-4 and the comparative examples 1 and 2 by using a laser particle size analyzer. The test results are shown in table 2 below.
TABLE 2
2. The antibacterial property of the plastic surface is tested by GB/T31402-2015/ISO 22196:2007 test method for antibacterial property of plastic surface. The PP plates of each example and each comparative example were tested for their antibacterial performance against escherichia coli and staphylococcus aureus, respectively, and expressed by an antibacterial performance value R. The test results are shown in table 3 below.
3. And (3) detection of roughness: the arithmetic mean Ra of the roughness profile of the surface of the PP sheet in each of the examples and comparative examples was measured using the GB/T14234 standard. The test results are shown in table 3 below.
TABLE 3
Note: the PP-1 plate is prepared from particles of glass antibacterial microbeads which are not subjected to a flame floating method and PP resin; the PP-2 plate is prepared from glass antibacterial micro-beads and PP resin.
Fig. 1 is a schematic diagram of glass antibacterial beads and particles thereof prepared in example 1 of the present invention, wherein fig. 1a is a schematic diagram of particles of glass antibacterial beads, and fig. 1b is a schematic diagram of glass antibacterial beads. The test results in tables 2 and 3 show that the glass antibacterial beads prepared by the flame floating method have better and uniform particle size distribution, and meanwhile, when the glass antibacterial resin product is prepared, the surface of the resin product is smooth and has low roughness, the antibacterial property is remarkably improved, and the improvement rate can reach 7-19%. According to the invention, the formula of the glass antibacterial micro-beads with excellent antibacterial property is combined with a flame floating method, and finally the glass antibacterial micro-beads are combined with a resin material, so that the glass antibacterial resin with good antibacterial property, smooth surface and difficult discoloration is prepared.
Claims (14)
1. The glass antibacterial microbead is characterized by comprising the following components in molar content:
B2O3：35~55mol%；
SiO2：15~40mol%；
alkali metal oxides: 2-25 mol%;
ZnO：5~30mol%；
antibacterial oxides: the antibacterial oxide is Ag2O and CuO, or Ag as the antibacterial oxide2O；
When the antibacterial oxide is Ag2O and CuO, the Ag2The content of O is 0.02-0.03 mol%, the content of CuO is 0-5 mol% but not 0, and the content of antibacterial oxide is 0.02-5 mol%;
when the antibacterial oxide is Ag2When O is, the Ag is2The content of O is 0.02-0.03 mol%;
alkaline earth metal oxide: 0-4 mol%;
the mol% is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads;
the glass antibacterial micro-beads are prepared by a flame floating method;
in the flame floating method, the temperature of flame is 920-990 ℃.
2. The antimicrobial glass microspheres of claim 1, wherein B is2O3The content of (A) is 40-51 mol%;
and/or, the SiO2The content of (A) is 20-35 mol%;
and/or the content of the alkali metal oxide is 5-15 mol%;
and/or the alkali metal oxide is Na2O and/or K2O；
And/or the content of ZnO is 8-20 mol%;
and/or, when the antibacterial oxide is Ag2And when the oxygen and the CuO are contained, the content of the CuO is 0.68-4.0 mol%.
3. The antimicrobial glass microspheres of claim 2, wherein B is2O3Is 40mol%, 45mol% or 51 mol%;
and/or, the SiO2In an amount of20mol%, 25mol%, 30mol% or 35 mol%;
and/or the content of the alkali metal oxide is 5mol%, 5.3mol%, 11mol% or 15 mol%;
and/or, the Na2The content of O is 3.3-15 mol%, and the mol% accounts for the total molar weight of the glass antibacterial micro-beads;
and/or, said K2The content of O is 1-3 mol%, and the mol% accounts for the total molar weight of the glass antibacterial micro-beads;
and/or the ZnO content is 8mol%, 15mol% or 20 mol%;
and/or, when the antibacterial oxide is Ag2O and CuO, the content of the CuO is 0.68mol%, 3mol% or 4 mol%;
and/or the alkaline earth metal oxide is MgO and/or CaO in kind.
4. The glass antimicrobial microbead according to claim 3, wherein the Na is2The content of O is 3.3mol%, 5mol%, 11mol% or 15mol%, and the mol% is the percentage of the total molar weight of the glass antibacterial micro-beads;
and/or, said K2The content of O is 2mol percent, and the mol percent is the percentage of the total molar weight of the glass antibacterial micro-beads;
and/or the content of the alkaline earth metal oxide is 2mol%, 3.97mol% or 4mol%, and the mol% is the percentage accounting for the total molar weight of the glass antibacterial micro-beads;
and/or the content of MgO is 1-4 mol%, and the mol% is the percentage of the total molar weight of the glass antibacterial micro-beads;
and/or the content of CaO is 2-3 mol%, and the mol% is the percentage of the total molar weight of the glass antibacterial micro-beads.
5. The glass antimicrobial microbead according to claim 4, wherein the MgO content is 3.97mol%, and the mol% is a percentage of the total molar amount of the glass antimicrobial microbead.
6. The glass antimicrobial microbead according to claim 1, which is characterized in thatCharacterized in that the glass antibacterial micro-beads consist of the following components in molar content: b2O3：40mol%、SiO2：25mol%、MgO：3.97mol%、Na2O：11mol%、ZnO：20mol%、Ag2O: 0.03mol percent, wherein the mol percent is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads;
or the glass antibacterial micro-beads consist of the following components in molar content: b is2O3：51mol%、SiO2：35mol%、Na2O：3.3mol%、K2O：2mol%、ZnO：8mol%、Ag2O: 0.02mol%, CuO: 0.68mol percent, wherein the mol percent is the percentage of the molar weight of each component in the total molar weight of the glass antibacterial micro-beads.
7. The glass antimicrobial microbeads of any one of claims 1-6, wherein the flame has a temperature of 950-970 ℃;
and/or, the particles of the glass antibacterial micro-beads are preheated before the flame floating method is carried out; the preheating temperature is 400 ℃;
and/or the time for carrying out the flame floating method on the particles of the glass antibacterial microbeads is 20-40 min;
and/or, cooling is carried out after the flame floating method, wherein the cooling is carried out to below 300 ℃;
wherein, the operation of sieving is also carried out after the cooling, and the mesh number of the sieve for sieving is 100 meshes or 200 meshes;
and/or, the preparation method of the particles of the glass antibacterial microbeads comprises the following steps: the glass antibacterial microspheres are prepared by mixing the raw materials according to the components, and then melting, cooling, drying and pulverizing the mixture to obtain the glass antibacterial microspheres.
8. The glass antimicrobial microbead according to claim 7, wherein the melting temperature is 1100-1350 ℃;
and/or the melting time is 20-120 min;
and/or the particle size of D10 of the glass antibacterial micro-bead particles is 2.5-3 microns before the flame floating method is carried out; the particle size of D50 of the glass antibacterial bead particles is 10-10.5 microns; the particle size of D99 of the glass antibacterial bead particles is 59-61 microns.
9. The glass antimicrobial microbeads of claim 8 wherein said melting temperature is 1200 ℃;
and/or, prior to performing the flame-floating method, the particles of the glass antimicrobial microbeads D10 have a particle size of 2.7 microns, 2.8 microns, or 2.9 microns; the particle size of D50 of the particles of the glass antibacterial micro-beads is 10.1 microns, 10.2 microns or 10.3 microns; the particle diameter of D99 of the particles of the glass antibacterial beads is 59.4 microns, 59.6 microns, 60.3 microns, or 61 microns.
10. A glass antibacterial resin comprising the glass antibacterial bead as set forth in any one of claims 1 to 9 and a resin material.
11. The glass antibacterial resin according to claim 10, wherein the mass ratio of the glass antibacterial beads to the resin material is (0.4-1.5): (98.5-99.6);
and/or the resin material is polypropylene resin, thermoplastic polyurethane or ABS resin; wherein the polypropylene resin is M800E; the grade of the ABS resin is PA-758 or PA-757K;
and/or the surface roughness of the glass antibacterial resin is 0.7-1 mu m;
and/or the preparation method of the glass antibacterial resin comprises the following steps: and mixing the glass antibacterial microspheres with the resin material, and then granulating and injection molding to obtain the antibacterial glass microsphere.
12. The glass antimicrobial resin according to claim 11, wherein a mass ratio of the glass antimicrobial beads to the resin material is 1: 99;
and/or the surface roughness of the glass antibacterial resin is 0.8 mu m.
13. The glass antimicrobial resin according to claim 11 or 12, wherein the granulation is extrusion granulation; wherein the temperature of the extrusion granulation is 195-205 ℃;
and/or the injection molding temperature is 210-230 ℃.
14. The glass antimicrobial resin of claim 13, wherein the temperature of the extrusion granulation is 200 ℃;
and/or the temperature of the injection molding is 220 ℃.
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| CN115028951A (en) * | 2022-06-16 | 2022-09-09 | 濮阳市中原石化实业有限公司 | Efficient composite additive for PU (polyurethane) |
| CN115636590B (en) * | 2022-10-08 | 2024-03-12 | 中建材玻璃新材料研究院集团有限公司 | Antibacterial glass powder, preparation method thereof and plastic antibacterial material |
| CN115594407B (en) * | 2022-10-20 | 2024-02-06 | 安徽正合雅聚新材料科技有限公司 | Silver-carrying glass antibacterial agent and antibacterial product with phosphorus-containing boroaluminosilicate glass as carrier |
| CN118290026A (en) * | 2024-04-07 | 2024-07-05 | 秦皇岛奥华玻璃有限公司 | High-performance ultra-white glass and preparation method thereof |
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