CN111011397B - Silver-containing inorganic antibacterial agent - Google Patents
Silver-containing inorganic antibacterial agent Download PDFInfo
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Abstract
The present invention provides an inorganic silver-containing antibacterial agent having excellent transparency, which is obtained by a silver-containing inorganic antibacterial agent represented by the formula AgaMbMgcRd (PO4) 2. nH2O containing magnesium pyrophosphate, wherein M is at least 1 kind of ion selected from alkali metal ions, ammonium ions, hydrogen ions and oxonium ions, R is a metal ion having a valence of 2, a, b, c, d and n are 3 or less, a and c are positive numbers, and the numbers satisfy 2.5 < (c + d) < 3 and a + b +2(c + d) ═ 6. The silver-containing inorganic antibacterial agent disclosed by the invention has the characteristics of excellent heat resistance, discoloration resistance, water washing resistance and processability when being applied to a high polymer material, and can be particularly applied to transparent products.
Description
Technical Field
The invention relates to the field of antibacterial agents, and particularly relates to a silver-containing inorganic antibacterial agent with excellent transparency, a preparation method thereof and an antibacterial product.
Background
The preparation of the silver-containing antibacterial agent generally adopts natural inorganic minerals with adsorption characteristics or artificially synthesized compounds as carriers, silver ions are loaded in the carriers in a liquid phase system in an ion exchange or adsorption mode, and then the silver-containing antibacterial agent is prepared in a high-temperature curing mode. The adsorption characteristics of natural inorganic minerals are often not ideal, which results in that the quantity of silver ions which can be adsorbed by the mineral is small, the binding force is poor, and the result shows that the mineral has low antibacterial efficiency, poor antibacterial water resistance and the defects of the self color and impurities of the natural mineral, and the mineral is often only applied to some lower-end high polymer material products. The adsorption performance and the self quality of some artificial synthetic inorganic carriers, such as zeolite, are higher than those of natural zeolite, but the adsorption amount is limited, and the silver content in the silver-containing artificial synthetic zeolite antibacterial agent on the market is one to five thousandths, and the silver content is easy to discolor. In addition, for example, the zirconium phosphate series silver-containing antibacterial agent, such as the layered zirconium phosphate series antibacterial agent, has a silver content of one percent to two percent, high antibacterial efficiency, but poor water resistance, such as the cubic zirconium phosphate series antibacterial agent, has a silver content of two percent to seven percent, relatively good water resistance, but too slow silver ion precipitation due to an excessively stable structure, so that the antibacterial efficiency is low, and when the silver-containing antibacterial agent is applied to a high molecular polymer, a larger additive amount is required to achieve a better antibacterial effect, so that the transparency of the high molecular product is further influenced. In particular, the refractive index of the silver-containing antibacterial agents of the zirconium phosphate series is much higher than that of the high molecular polymer, and the transparency is poor. The glass silver-containing antibacterial agent is greatly improved in transparency as compared with the above silver-containing antibacterial agent. Because the glass silver-carrying antibacterial agent is obtained by melting, quenching and crushing, the glass silver-carrying antibacterial agent is difficult to crush to be within 3 microns, and the powder is easy to discolor when the crushed particle size is finer. The ultrafine powder obtained by pulverization tends to have irregular particle shapes and its transparency is also affected. Even if the silver-loaded glass antibacterial agent has the defects, the silver-loaded glass antibacterial agent still is a main solution for preparing antibacterial transparent polymer material products at present.
Therefore, there is a need to design an inorganic silver-containing antibacterial agent to solve the above problems.
Disclosure of Invention
The present invention provides a silver-containing inorganic antibacterial agent and an antibacterial processed product having excellent transparency, excellent processability and excellent water resistance.
The inventors have conducted intensive studies and, as a result, found that: the problems of the conventional silver-containing inorganic antibacterial agents mentioned above can be solved by an antibacterial agent represented by the following formula [ 1 ] containing magnesium pyrophosphate (Mg 2P2O 7).
An inorganic silver-containing antibacterial agent represented by the following formula [ 1 ] containing magnesium pyrophosphate,
AgaMbMgcRd(PO4)2·nH2O〔1〕
in the formula [ 1 ], M is at least 1 ion selected from alkali metal ions, ammonium ions, hydrogen ions and oxonium ions, R is a metal ion having a valence of 2, a, b, c, d and n are 3 or less, a and c are positive numbers, and the numbers satisfy 2.5 < (c + d) < 3, a + b +2(c + d) ═ 6.
Further, the refractive index is 1.46 to 1.60.
Further, the silver-containing inorganic antibacterial agent represented by the formula [ 1 ] having an electrical conductivity of 15 to 500. mu.S when suspended in water, which is obtained by wet synthesis or hydrothermal synthesis, is subjected to heat treatment at 600 to 900 ℃.
Further, the bulk specific gravity before the heat treatment is 0.7 to 1.5 (g/ml).
An antibacterial processed article excellent in transparency, which contains a silver inorganic antibacterial agent.
The invention has the beneficial effects that:
compared with the existing silver-carrying antibacterial agent, the silver-containing inorganic antibacterial agent can be applied to transparent products, endows the products with antibacterial function, basically does not influence the transparency of the products, is superior to the existing known antibacterial agent, and also has obvious improvement on the aspects of antibacterial efficiency, water resistance and discoloration resistance.
Drawings
FIG. 1 is a scanning electron microscope image of the silver-containing inorganic antibacterial agent obtained in example 1.
FIG. 2 is a scanning electron micrograph of the silver-containing inorganic antibacterial agent obtained in example 3.
Detailed Description
The silver-containing inorganic antibacterial agent of the present invention contains magnesium pyrophosphate (Mg)2P2O7) The antibacterial agent represented by the following formula [ 1 ] can solve the problems of the conventional silver-containing inorganic antibacterial agents mentioned above.
AgaMbMgcRd(PO4)2·nH2O 〔1〕
In the formula [ 1 ], M is at least 1 ion selected from alkali metal ions, ammonium ions, hydrogen ions and oxonium ions, R is a metal ion having a valence of 2, a, b, c, d and n are 3 or less, a and c are positive numbers, and the numbers satisfy 2.5 < (c + d) < 3, a + b +2(c + d) ═ 6.
In the formula [ 1 ], a is 0 < a, preferably 0.01 or more, more preferably 0.03 or more,
and a is preferably 0.6 or less, more preferably 0.3 or less. When a is less than 0.01, the antibacterial efficiency is low. When a is more than 0.6, the silver content is too high, which causes significant discoloration problems during preparation and application, and affects transparency.
In the formula [ 1 ], in order to obtain a silver-containing antibacterial agent having more excellent discoloration resistance, M is more preferably an alkali metal ion. b is different from M in the optimum value depending on the kind of the alkali metal ion, ammonium ion, hydrogen ion or oxonium ion. Is 0 < b, preferably 0.01 or more. In addition, b is less than 1, preferably less than 0.6, and more preferably 0.4 or less. When the value of b is large, a problem of discoloration occurs.
In the formula [ 1 ], R is preferably a divalent metal ion containing at least one or more of a zinc ion, a calcium ion and a manganese ion, and d is preferably 0.2 or less, more preferably 0.001 to 0.15, further preferably 0.005 to 0.10, in order to obtain a silver-containing antibacterial agent having further excellent transparency.
In the formula [ 1 ], n is preferably 1 or less, more preferably in the range of 0.01 to 0.5, particularly preferably 0.03 to 0.3. When n exceeds 2, the water content is large, and foaming, hydrolysis, etc. are liable to occur during processing, which is not preferable.
The silver-containing inorganic antibacterial agent represented by the formula [ 1 ] may be the following.
Ag0.03Na0.03H0.3(H3O)0.2Mg2.7Zn0.02(PO4)2·0.15H2O
Ag0.10Na0.04H0.1(H3O)0.1Mg2.8Zn0.03(PO4)2·0.05H2O
Ag0.16Na0.14K0.03H0.45Mg2.6Mn0.01(PO4)2·0.15H2O
Ag0.17Na0.15H0.02(H3O)0.06Mg2.6Ca0.2(PO4)2·0.15H2O
Ag0.19Na0.05K0.02Mg2.72Zn0.15(PO4)2·0.25H2O
Ag0.17Na0.05K0.02H0.02Mg2.62Zn0.25(PO4)2·0.15H2O
Ag0.45Na0.2H0.21Mg2.55Zn0.02(PO4)2·0.05H2O
Ag0.55K0.1H0.15Mg2.59Zn0.01(PO4)2·0.15H2O
Ag0.12Na0.20K0.3Mg2.52Zn0.05Ca0.12(PO4)2·0.15H2O
Ag0.45Na0.12H0.02(H3O)0.05Mg2.65Zn0.02(PO4)2·0.05H2O
Ag0.55Na0.1H0.07Mg2.48Zn0.11Ca0.02Mn0.03(PO4)2·0.15H2O
The silver-containing inorganic antibacterial agent of the present invention is a silver-containing inorganic antibacterial agent represented by the above formula [ 1 ] containing zirconium pyrophosphate (MgP2O 7).
Magnesium pyrophosphate exists as a single body with the silver-based inorganic antibacterial agent particles of the above formula [ 1 ], and is in a state of inseparable, and is not a substance obtained by mixing the respective compounds.
The silver-containing inorganic antibacterial agent represented by the formula [ 1 ] of the present invention is obtained by ion-exchanging an aqueous solution containing silver nitrate in an amount of 0.5 to 0.99 multiplied by the coefficient b1 of the formula [ 2 ] with respect to 1 mole of the compound represented by the following formula [ 2 ], and then performing heat treatment.
Ab1Bc1MgeZnf(PO4)2·nH2O 〔2〕
(in the formula [ 2 ], A is a sodium ion or a potassium ion, B is an ammonium ion and/or a hydrogen ion, B1, c1, e and f are positive numbers, and a number satisfying 2.5 < (e + f) < 3, B1+ c1+2(e + f) > 6.)
To obtain a monodispersed material of formula [ 2 ] having a particle size of less than 5 μm, the synthesis process is preferably solid phase ball milling, and a small amount of pure water or an organic solvent containing a surfactant is added during the ball milling. In a specific method for synthesizing the substance of the formula [ 2 ], the divalent metal compound, ammonia or a salt thereof, phosphoric acid or a salt thereof, and the like are contained in predetermined amounts and ball-milled at a temperature of 50 ℃ or higher. And fully washing the substances obtained after ball milling by using pure water, and then loading silver ions. The supported silver-containing substance was further filtered, washed with water to a predetermined conductivity, dried, and gently pulverized to obtain white monodisperse silver-containing magnesium phosphate.
In order to obtain the substance represented by the formula [ 2 ], it is preferable to mix a sparingly soluble compound of a divalent metal, ammonium dihydrogen phosphate, sodium dihydrogen phosphate or a composition of sodium dihydrogen phosphate, and add a small amount of pure water containing a surfactant such as polyethylene glycol or polyethyleneimine, followed by ball milling reaction, the ball milling time is preferably 4 to 12 hours, and the temperature is preferably 50 ℃ to 100 ℃.
In order to obtain the substance represented by the formula [ 2 ], a water-soluble salt of a soluble divalent metal may be selected, and mixed with a prescribed amount of polyphosphoric acid, phosphoric acid, sodium phosphate, potassium phosphate or ammonium phosphate, the PH is adjusted to 4 to 6 by adding ammonia water or sodium hydroxide, the obtained composition is reacted in an oven at 50 ℃ or higher for 6 to 18 hours, more preferably, the obtained composition is added with a small amount of a surfactant such as polyethylene glycol or polyethyleneimine and then subjected to a ball milling reaction, the ball milling time is preferably 4 to 12 hours, and the temperature is preferably 50 ℃ or higher and 100 ℃ or lower.
In order to obtain the substance represented by the formula [ 2 ], the molar ratio of the divalent metal ion and the phosphorus source (the phosphorus source is set to 1) in the present invention is more than 1.2 and less than 1.5.
Further, the substance represented by the formula [ 2 ] has a high silver ion-supporting rate, and the supported adsorption time is preferably 10 minutes to 3 hours, and after the silver ion is supported, it is preferably washed with deionized water or the like. After the washing, the silver-containing inorganic antibacterial agent represented by the formula [ 1 ] containing magnesium pyrophosphate at a certain concentration can be obtained by conducting filtration drying and heat treatment in a state where the volume specific gravity is adjusted to an appropriate value.
The washing with water is preferably carried out to a suitable degree of washing, which means that the conductivity when the particles are suspended in deionized water is 15. mu.S or more and 500. mu.S or less, more preferably 30. mu.S or less
Upper 400. mu.S or less.
Drying the washed solid component, opening the agglomeration to obtain uniformly dispersed powder, controlling the volume specific gravity to be 0.7-1.5g/ml, and then carrying out heat treatment. The heat treatment may be carried out at 600 ℃ to 900 ℃, preferably 650 ℃ to 850 ℃,
the longer the heat treatment is performed, the more the discoloration resistance is improved, and uniform properties can be obtained,
however, it is uneconomical if it is too long, and therefore it is preferably 1 hour or more, and 2 hours is preferable for improving discoloration resistance
The time is preferably from 60 hours to more, more preferably from 4 hours to 36 hours.
After the heat treatment, the ultrafine particles of the silver-containing inorganic antibacterial agent of the present invention may be sintered into particles of more than 10 μm, and may be refined by using a jet mill.
The silver-based inorganic antibacterial agent of the present invention may be used in any form, including, but not limited to, mixing with other components or compounding with other materials, as appropriate depending on the application. For example, the antibacterial finishing agent can be prepared into antibacterial master batches to be added into a high polymer material to prepare an antibacterial high polymer material product, or can be prepared into an antibacterial coating by adding a dispersion liquid containing powder into the coating, or can be a natural fabric antibacterial finishing agent, or an antibacterial spray, or can be an antistaling agent.
If necessary, a mixed functional aid having an antibacterial function may be prepared by mixing the above-mentioned materials with other antibacterial agents, deodorants, antiviral agents, antiallergic agents, photocatalysts and the like.
The silver-based inorganic antibacterial agent of the present invention may be mixed with various additives as necessary for improving processability and other physical properties of the silver-based inorganic antibacterial agent mixed into a resin. Specifically, there is zinc oxide titanium oxide
And the like; inorganic ion exchangers such as zirconium phosphate and zeolite; dyes, antioxidants, light stabilizers,
Flame retardant, antistatic agent, foaming agent, impact-resistant reinforcer, lubricant such as glass fiber and metal soap,
Moisture-proof agent, extender, coupling agent, nucleating agent, fluidity improver, deodorant, wood powder, dust-proof agent
An antifouling agent, an antirust agent, metal powder, an ultraviolet absorber, an ultraviolet screening agent, and the like.
By blending the silver-based inorganic antibacterial agent of the present invention with a resin, an antibacterial resin set can be easily obtained
A compound (I) is provided. The kind of the resin which can be used is not particularly limited, and may be a natural resin, a synthetic resin, a polyester resin, a polyamide resin, a,
Any of semi-synthetic resins, thermoplastic resins and thermosetting resins may be used
One, preparing into antibacterial products, such as antibacterial toilet cover plate, antibacterial preservative film, antibacterial chopping board, etc.
In particular, the invention can be prepared into water-resistant polymer material products, such as water pipes.
In particular, the invention can be used for preparing superfine antibacterial fiber and antibacterial transparent products.
The mixing ratio of the antibacterial resin composition of the silver-based inorganic antibacterial agent of the present invention is relative to the antibacterial activity
The amount of the bacterial resin composition is preferably 0.1 to 0.8 part by weight, more preferably 0.3 to 0.6 part by weight, per 100 parts by weight of the bacterial resin composition. The antibacterial resin mother particle is preferably 8 to 20 parts by weight, more preferably 10 to 15 parts by weight, per 100 parts by weight.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the invention, an important evaluation index is refractive index, but no standard test method exists for the refractive index of specific powder, the refractive index of the silver-containing inorganic antibacterial agent is qualitatively represented by evaluating the refractive index of various high polymer materials containing 10% of powder, for example, polypropylene with the refractive index of 1.46 is selected as a reference sample, the increase value of the refractive index of the polypropylene material added with 10% of powder is measured to be within 0.02, and then the refractive index of the powder is represented to be close to 1.46. The transparency of different powders can be represented by the increased value of the refractive index of the polypropylene material containing 10% of the powder, and meanwhile, the transparency of different powders can be represented according to the light transmittance. The invention selects polypropylene (PP) with a refractive index of 1.46, polymethyl methacrylate (PMMA) with a refractive index of 1.49, polyvinyl chloride (PVC) with a refractive index of 1.52, Polycarbonate (PC) with a refractive index of 1.58 and Polystyrene (PS) with a refractive index of 1.60 as reference samples respectively. Although the method for measuring refractive index of the present invention has drawbacks, it has been shown through a large number of experiments by the present inventors that it is the most effective method for measuring refractive index of powder at present, and particularly, it is most effective for the monodisperse ultrafine powder prepared by the present invention.
In the invention, the antibacterial and mildewproof detection is carried out according to the GB21551-20102 standard, and the Minimum Inhibitory Concentration (MIC) is carried out according to the minimum inhibitory concentration determination test method in the disinfection technical specification 2017.
Particle size was measured on a volume basis using a laser diffraction particle size distribution.
Light transmittance was measured using an integrating sphere haze meter.
The monodispersity of the powder is represented by a scanning electron microscope picture.
The composition of the powder is mainly characterized by X-ray energy spectrum analysis, the amount of oxonium ions is measured and calculated by thermal analysis on the weight loss at 190 ℃ of 160-DEG C, and the amount of ammonia is measured by an indophenol method.
In order to better show the advancement of the invention, the invention particularly selects the silver-series antibacterial agent sold in the domestic market at present as a comparison sample, and the two types of antibacterial agents are respectively as follows: cubic zirconium phosphate silver-carrying antibacterial agent (JD) manufactured by Xiamen jin company, layered zirconium phosphate silver-carrying antibacterial agent (RH) manufactured by Shanghai Runhe company, glass silver-carrying antibacterial agent (XY) manufactured by Nippon Xinya company, and zeolite silver-carrying antibacterial agent (JEMK) manufactured by Nippon Jieshou Meike company.
Unless otherwise specified,% represents mass% and ppm represents mass ppm.
Example 1
Adding 0.05 mol of magnesium hydroxide with the grain diameter of 1 micron, 0.0039 mol of zinc chloride with the grain diameter of 15 microns, 0.0039 mol of ammonium chloride with the grain diameter of 15 microns and 0.0059 mol of sodium chloride with the grain diameter of 20 microns into a mortar respectively, grinding and mixing uniformly, adding 5 drops of polyethylene glycol 400 for continuous grinding, then adding 0.041 mol of phosphoric acid for continuous grinding.
It was found that the mixture thickened slowly from wet to pasty and in a fine state, then became hard and moist.
And (3) putting the damp blocky mixture into a ball mill for ball milling, controlling the temperature in a ball mill tank to be 50 ℃, taking out after 6 hours, carefully cleaning the obtained product, and drying at 110 ℃, thereby synthesizing the magnesium phosphate compound containing sodium ions and ammonium ions.
The compound has a composition formula of
Na0.3(NH4)0.2Mg2.55Zn0.2(PO4)2·0.09H2O。
To the resulting compound, 70ml of an aqueous solution of deionized water in which 0.0042 mol of silver nitrate was dissolved was added, and the mixture was stirred at room temperature for 2 hours to complete the loading of silver ions. The slurry having silver supported thereon was filtered, washed with water, and washed until the conductivity of the filtrate became 220. mu.S, and the solid content was dried at 110 ℃ to adjust the bulk specific gravity to 1.01 g/ml.
The composition formula obtained by measuring the amounts of the respective components of the dry solid content is as follows:
Ag0.15Na0.23H0.12Mg2.5Zn0.25(PO4)2·0.13H2O
and then, treating the silver-containing inorganic antibacterial agent in a high-temperature furnace at 650 ℃ for 16 hours, naturally cooling the silver-containing inorganic antibacterial agent, and crushing the silver-containing inorganic antibacterial agent to obtain the silver-containing inorganic antibacterial agent, wherein the dispersion morphology of the silver-containing inorganic antibacterial agent is shown in a figure 1, and the performance characterization of the silver-containing inorganic antibacterial agent is shown in an attached table 1.
Example 2
A support material having the following composition formula obtained in example 1 was used.
Na0.3(NH4)0.2Mg2.55Zn0.2(PO4)2·0.09H2O
70ml of an aqueous solution of deionized water in which 0.0084 mol of silver nitrate was dissolved was added to the carrier material, and the mixture was stirred at room temperature for 2 hours to complete the loading of silver ions. The slurry having silver supported thereon was filtered, washed with water, and washed until the filtrate had a conductivity of 360. mu.S, and the solid content was dried at 110 ℃ to adjust the bulk specific gravity to 1.12 g/ml.
The composition formula obtained by measuring the amounts of the respective components of the dry solid content is as follows:
Ag0.3Na0.11H0.09Mg2.5Zn0.25(PO4)2·0.13H2O
and treating the mixture for 10 hours at 900 ℃ in a high-temperature furnace, naturally cooling the mixture, and crushing the mixture to obtain the silver-containing inorganic antibacterial agent.
Example 3
0.06 mole of magnesium sulfate heptahydrate with the particle size of 15 microns, 0.00046 mole of zinc chloride with the particle size of 15 microns and 0.0083 mole of ammonium chloride with the particle size of 15 microns are respectively added into a mortar, ground and mixed uniformly, 5 drops of polyethylene glycol 400 are added for continuous grinding, 0.046 mole of disodium hydrogen phosphate dodecahydrate is then added continuously for continuous grinding, ammonia water is added continuously for dropwise adding, and the pH value is controlled to be 5.2.
The mixture was found to be very thin paste-like.
And (3) putting the pasty mixture into a ball mill for ball milling, controlling the temperature in a ball milling tank at 70 ℃, taking out after 6 hours, carefully cleaning the obtained product, and drying at 110 ℃, thereby synthesizing the magnesium phosphate compound containing sodium ions and ammonium ions.
The compound has a composition formula of
Na0.4(NH4)0.36Mg2.6Zn0.02(PO4)2·0.08H2O。
To the resulting compound, 70ml of an aqueous solution of deionized water in which 0.0055 mol of silver nitrate was dissolved was added, and the mixture was stirred at room temperature for 2 hours to complete the loading of silver ions. The slurry having silver supported thereon was filtered, washed with water, and washed until the filtrate had a conductivity of 360. mu.S, and the solid content was dried at 110 ℃ to adjust the bulk specific gravity to 1.2 g/ml.
The composition formula obtained by measuring the amounts of the respective components of the dry solid content is as follows:
Ag0.23Na0.33H0.2Mg2.6Zn0.02(PO4)2·0.12H2O
and then, the silver-containing inorganic antibacterial agent is obtained after being treated for 12 hours at 700 ℃ in a high-temperature furnace, naturally cooled and crushed, the dispersion morphology of the silver-containing inorganic antibacterial agent is shown in the attached figure 2, and the performance representation of the silver-containing inorganic antibacterial agent is shown in the attached table 1.
Example 4
Adding 0.06 mol of magnesium hydroxide with the grain diameter of 1 micron, 0.00046 mol of calcium hydroxide with the grain diameter of 1 micron and 0.0092 mol of sodium chloride with the grain diameter of 15 microns into a mortar respectively, grinding and mixing uniformly, adding 6 drops of polyethyleneimine, continuously grinding, then adding 0.046 mol of ammonium dihydrogen phosphate, continuously grinding, and slowly adding deionized water until the mixture is viscous and has certain toughness.
And (2) putting the mixture into a ball mill for ball milling, controlling the temperature in the ball mill to be 70 ℃, taking out after 6 hours, carefully cleaning the obtained product, and drying at 110 ℃, thereby synthesizing the magnesium phosphate compound containing sodium ions and ammonium ions.
The compound has a composition formula of
Na0.4(NH4)0.36Mg2.6Ca0.02(PO4)2·0.05H2O。
To the resulting compound, 70ml of an aqueous solution of deionized water in which 0.007 mol of silver nitrate was dissolved was added, and the mixture was stirred at room temperature for 2 hours to complete the loading of silver ions. The slurry having silver supported thereon was filtered, washed with water, and washed until the filtrate had a conductivity of 60. mu.S, and the solid content was dried at 110 ℃ to adjust the bulk specific gravity to 0.92 g/ml.
The composition formula obtained by measuring the amounts of the respective components of the dry solid content is as follows:
Ag0.23Na0.33H0.2Mg2.6Ca0.02(PO4)2·0.15H2O
and then, the silver-containing inorganic antibacterial agent is obtained after being treated for 12 hours at 900 ℃ in a high-temperature furnace, naturally cooled and crushed, the refractive index of the silver-containing inorganic antibacterial agent is 1.49, and the dispersion morphology of the silver-containing inorganic antibacterial agent is shown in figure 1.
Example 5
Adding 0.06 mol of magnesium hydroxide with the particle size of 1 micron and 0.00043 mol of calcium hydroxide with the particle size of 1 micron into a mortar respectively, grinding and mixing uniformly, adding 6 drops of polyethyleneimine, continuously grinding, then adding a mixture of ground 0.043 mol of ammonium dihydrogen phosphate and 0.0043 mol of potassium dihydrogen phosphate, further grinding, and slowly adding deionized water until the mixture is viscous and has certain toughness.
And (2) putting the viscous mixture into a ball mill for ball milling, controlling the temperature in the ball mill to be 70 ℃, taking out after 6 hours, carefully cleaning the obtained product, and drying at 110 ℃, thereby synthesizing the magnesium phosphate compound containing potassium ions and ammonium ions.
The compound has a composition formula of
K0.2(NH4)0.16Mg2.8Ca0.02(PO4)2·0.05H2O。
To the resulting compound, 70ml of an aqueous solution of deionized water in which 0.0036 mol of silver nitrate was dissolved was added, and the mixture was stirred at room temperature for 2 hours to complete the loading of silver ions. The slurry having silver supported thereon was filtered, washed with water, and washed until the conductivity of the filtrate became 120. mu.S, and the solid matter dried at 110 ℃ was adjusted to a bulk specific gravity of 0.62 g/ml.
The composition formula obtained by measuring the amounts of the respective components of the dry solid content is as follows:
Ag0.17K0.11H0.1Mg2.8Ca0.02(PO4)2·0.08H2O
and then, treating the silver-containing inorganic antibacterial agent for 18 hours in a high-temperature furnace at 800 ℃, naturally cooling the silver-containing inorganic antibacterial agent, and crushing the silver-containing inorganic antibacterial agent to obtain the silver-containing inorganic antibacterial agent, wherein the performance characteristics of the silver-containing inorganic antibacterial agent are shown in the attached table 1.
Example 6
Adding 0.06 mol of magnesium hydroxide with the particle size of 1 micron and 0.00087 mol of manganese sulfate with the particle size of 10 microns into a mortar respectively, grinding and mixing uniformly, adding 6 drops of PEG400, continuing grinding, then adding a mixture of ground 0.043 mol of ammonium dihydrogen phosphate and 0.0043 mol of sodium dihydrogen phosphate, continuing grinding, and slowly adding deionized water until the mixture is viscous and has certain toughness.
And (3) putting the viscous mixture into a ball mill for ball milling, controlling the temperature in the ball mill to be 80 ℃, taking out the viscous mixture after 4 hours, carefully cleaning the obtained product, and drying the product at 110 ℃, thereby synthesizing the magnesium phosphate compound containing sodium ions and ammonium ions.
The compound has a composition formula of
Na0.2(NH4)0.2Mg2.76Mn0.04(PO4)2·0.05H2O。
To the resulting compound, 70ml of an aqueous solution of deionized water in which 0.0026 mol of silver nitrate was dissolved was added, and the mixture was stirred at room temperature for 2 hours to complete the loading of silver ions. The slurry having silver supported thereon was filtered, washed with water, and washed until the conductivity of the filtrate became 190. mu.S, and the solid content was dried at 110 ℃ to adjust the bulk specific gravity to 1.22 g/ml.
The composition formula obtained by measuring the amounts of the respective components of the dry solid content is as follows:
Ag0.12Na0.08H0.2Mg2.76Mn0.04(PO4)2·0.15H2O
and then, treating the silver-containing inorganic antibacterial agent in a high-temperature furnace at 650 ℃ for 20 hours, naturally cooling the silver-containing inorganic antibacterial agent, and crushing the silver-containing inorganic antibacterial agent to obtain the silver-containing inorganic antibacterial agent, wherein the dispersion morphology of the silver-containing inorganic antibacterial agent is shown in the attached figure 1.
Comparative example 1
Adding 0.054 mol zinc oxide with grain diameter of 1 micron, 0.0039 mol ammonium chloride with grain diameter of 15 microns and 0.0059 mol sodium chloride with grain diameter of 20 microns into a mortar respectively, grinding and mixing uniformly, adding 5 drops of polyethylene glycol 400 for continuous grinding, then adding 0.041 mol phosphoric acid for continuous grinding.
It was found that the mixture thickened slowly from wet to pasty and in a fine state, then became hard and moist.
And (3) putting the damp blocky mixture into a ball mill for ball milling, controlling the temperature in a ball mill tank to be 50 ℃, taking out the damp blocky mixture after 4 hours, carefully cleaning the obtained product, and drying the product at 110 ℃, thereby synthesizing the magnesium phosphate compound containing sodium ions and ammonium ions.
The compound has a composition formula of
Na0.3(NH4)0.2Zn2.75(PO4)2·0.09H2O。
To the resulting compound, 70ml of an aqueous solution of deionized water in which 0.0042 mol of silver nitrate was dissolved was added, and the mixture was stirred at room temperature for 2 hours to complete the loading of silver ions. The slurry having silver supported thereon was filtered, washed with water, and washed until the conductivity of the filtrate became 220. mu.S, and the solid content was dried at 110 ℃ to adjust the bulk specific gravity to 1.01 g/ml.
The composition formula obtained by measuring the amounts of the respective components of the dry solid content is as follows:
Ag0.15Na0.23H0.12Zn2.75(PO4)2·0.13H2O
and then, the silver-containing inorganic antibacterial agent is obtained after being treated for 16 hours at 650 ℃ in a high-temperature furnace, naturally cooled and crushed, and the performance characteristics of the silver-containing inorganic antibacterial agent are shown in the attached table 1.
Comparative example 2
0.0605 mol of manganese sulfate heptahydrate with the particle size of 15 micrometers and 0.0083 mol of ammonium chloride with the particle size of 15 micrometers are respectively added into a mortar, ground and mixed uniformly, 5 drops of polyethylene glycol 400 are added for continuous grinding, 0.046 mol of disodium hydrogen phosphate dodecahydrate is added successively, the grinding is continued, ammonia water is added continuously, and the pH value is controlled to be 5.2.
The mixture was found to be very thin paste-like.
And (3) putting the pasty mixture into a ball mill for ball milling, controlling the temperature in a ball milling tank at 70 ℃, taking out after 6 hours, carefully cleaning the obtained product, and drying at 110 ℃, thereby synthesizing the magnesium phosphate compound containing sodium ions and ammonium ions.
The compound has a composition formula of
Na0.4(NH4)0.36Mn2.62(PO4)2·0.08H2O。
To the resulting compound, 70ml of an aqueous solution of deionized water in which 0.0055 mol of silver nitrate was dissolved was added, and the mixture was stirred at room temperature for 2 hours to complete the loading of silver ions. The slurry having silver supported thereon was filtered, washed with water, and washed until the filtrate had a conductivity of 360. mu.S, and the solid content was dried at 110 ℃ to adjust the bulk specific gravity to 1.2 g/ml.
The composition formula obtained by measuring the amounts of the respective components of the dry solid content is as follows:
Ag0.23Na0.33H0.2Mn2.62(PO4)2·0.12H2O
and then treating the silver-containing inorganic antibacterial agent in a high-temperature furnace at 700 ℃ for 12 hours, naturally cooling the silver-containing inorganic antibacterial agent, and crushing the silver-containing inorganic antibacterial agent to obtain the silver-containing inorganic antibacterial agent, wherein the performance characteristics of the silver-containing inorganic antibacterial agent are shown in the attached table 1.
Comparative example 3
0.06 mol of magnesium hydroxide with the particle size of 1 micron, 0.00046 mol of calcium hydroxide with the particle size of 1 micron, 0.0092 mol of sodium chloride with the particle size of 15 microns, 6 drops of polyethyleneimine and 0.046 mol of ammonium dihydrogen phosphate are sequentially added into a beaker filled with 100 ml of pure water for continuous grinding. The temperature in the beaker was controlled at 70 c under uniform stirring, and after 10 hours, a solid product was obtained by filtration, and the obtained product was carefully washed and dried at 110 c, whereby a magnesium phosphate compound containing sodium ions and ammonium ions was synthesized.
The compound has a composition formula of
Na0.4(NH4)0.36Mg2.6Ca0.02(PO4)2·0.05H2O。
To the resulting compound, 70ml of an aqueous solution of deionized water in which 0.007 mol of silver nitrate was dissolved was added, and the mixture was stirred at room temperature for 2 hours to complete the loading of silver ions. The slurry having silver supported thereon was filtered, washed with water, and washed until the filtrate had a conductivity of 60. mu.S, and the solid content was dried at 110 ℃ to adjust the bulk specific gravity to 1.8 g/ml.
The composition formula obtained by measuring the amounts of the respective components of the dry solid content is as follows:
Ag0.18Na0.38H0.2Mg2.6Ca0.02(PO4)2·0.15H2O
and then, the silver-containing inorganic antibacterial agent is obtained after being treated for 12 hours at 900 ℃ in a high-temperature furnace, naturally cooled and crushed, and the performance characteristics of the silver-containing inorganic antibacterial agent are shown in the attached table 1.
Comparative example 4
Adding 0.06 mol of magnesium hydroxide with the particle size of 1 micron and 0.00043 mol of calcium hydroxide with the particle size of 1 micron into a mortar respectively, grinding and mixing uniformly, adding 6 drops of polyethyleneimine, grinding continuously, adding a mixture of ground 0.043 mol of ammonium dihydrogen phosphate and 0.016 mol of potassium dihydrogen phosphate, grinding continuously, and slowly adding deionized water until the mixture is viscous and has certain toughness.
And (2) putting the viscous mixture into a ball mill for ball milling, controlling the temperature in the ball mill to be 70 ℃, taking out after 6 hours, carefully cleaning the obtained product, and drying at 110 ℃, thereby synthesizing the magnesium phosphate compound containing potassium ions and ammonium ions.
The compound has a composition formula of
K0.68(NH4)0.18Mg2.55Ca0.02(PO4)2·0.05H2O。
To the resulting compound, 70ml of an aqueous solution of deionized water in which 0.0036 mol of silver nitrate was dissolved was added, and the mixture was stirred at room temperature for 2 hours to complete the loading of silver ions. The slurry having silver supported thereon was filtered, washed with water, and washed until the conductivity of the filtrate became 120. mu.S, and the solid matter dried at 110 ℃ was adjusted to a bulk specific gravity of 0.62 g/ml.
The composition formula obtained by measuring the amounts of the respective components of the dry solid content is as follows:
Ag0.17K0.6H0.09Mg2.55Ca0.02(PO4)2·0.08H2O
and then, treating the silver-containing inorganic antibacterial agent for 18 hours in a high-temperature furnace at 800 ℃, naturally cooling the silver-containing inorganic antibacterial agent, and crushing the silver-containing inorganic antibacterial agent to obtain the silver-containing inorganic antibacterial agent, wherein the performance characteristics of the silver-containing inorganic antibacterial agent are shown in the attached table 1.
TABLE 1 characterization of silver-containing inorganic antimicrobial agents
As is clear from the results shown in Table 1, the silver-containing antibacterial agent of the present invention has significant advantages in terms of both particle size and refractive index, and has a higher antibacterial performance at a lower silver elution rate.
Example 7: evaluation of the use in Polypropylene
Mixing the silver-containing antibacterial agent and the polypropylene granules according to the addition of zero four percent, granulating by a double-screw granulator, and then injection molding into a sheet with the thickness of 1 mm.
TABLE 2 evaluation of the use in polypropylene
Example 8: evaluation of use in Nylon
Evaluation of use in nylon:
and mixing the silver-containing antibacterial agent and the nylon material according to the addition of zero four percent, granulating by a double-screw granulator, and then spinning. Color difference the color value of the spun yarn was measured with a colorimeter, displayed in the Hunter-Lab color system defined in JIS Z8730-1980, and compared with a blank yarn, the color difference Δ E (Delta E) was calculated. The spinning processability was evaluated by a breaking test, and it was evaluated by whether or not breaking occurred before 1 package of the undrawn yarn wound in a volume of 6kg was obtained.
TABLE 3 evaluation in Nylon
Example 8: evaluation in polyethylene terephthalate (PET)
And mixing the silver-containing antibacterial agent and the PET material according to the addition of zero four percent, granulating by a double-screw granulator, and then casting into a film with the thickness of 150 microns.
TABLE 4 evaluation in PET
From the results of examples 7, 8 and 9, it was confirmed that the silver-containing inorganic antibacterial agent of the present invention is superior to the conventional silver-containing inorganic antibacterial agent not only in antibacterial performance after a water resistance test but also in processability and discoloration resistance in plastic product processing.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (5)
1. An inorganic silver-containing antibacterial agent represented by the following formula [ 1 ] containing magnesium pyrophosphate,
AgaMbMgcRd(PO4)2·nH2O 〔1〕
in the formula [ 1 ], M is at least 1 ion selected from alkali metal ions, ammonium ions, hydrogen ions and oxonium ions, R is a metal ion having a valence of 2, a, b, c, d and n are 3 or less, a and c are positive numbers, and the numbers satisfy 2.5 < (c + d) < 3, a + b +2(c + d) ═ 6.
2. The silver-containing inorganic antimicrobial agent of claim 1, wherein the refractive index of the antimicrobial agent is from 1.46 to 1.60.
3. A process for producing a silver-containing inorganic antibacterial agent, characterized by heat-treating a silver-containing inorganic antibacterial agent represented by the formula [ 1 ] having an electrical conductivity of 15 to 500 [ mu ] S when suspended in water, which is obtained by wet synthesis or hydrothermal synthesis, at 600 to 900 ℃.
4. The method of claim 3, wherein the bulk specific gravity before the heat treatment is 0.7 to 1.5 g/ml.
5. An antibacterial processed article excellent in transparency, which contains the silver-containing inorganic antibacterial agent according to claim 1 or 2.
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