阅读说明：本技术 复合金属胶体抗菌的有机人造石及其抗菌剂的制备方法 (Composite metal colloid antibacterial organic artificial stone and preparation method of antibacterial agent thereof ) 是由 高忠麟 舒诚 于 2020-08-12 设计创作，主要内容包括：本发明公开了一种复合金属胶体抗菌的有机人造石及其抗菌剂的制备方法。包括抗菌粘结液,所述抗菌粘结液包括复合金属胶体抗菌剂,所述复合金属胶体抗菌剂包括包括羟基磷酸锆微粉、银原子、铜原子和纳米二氧化钛；其中,所述纳米二氧化钛的表面微孔吸附有所述银原子和铜原子胶体,所述羟基磷酸锆微粉的表面吸附有银原子、铜原子和纳米二氧化钛胶体；所述银原子作为活化剂,所述铜原子作为待激活抗菌剂,所述纳米二氧化钛作为紫外杀菌体。所述复合金属胶体抗菌剂,含有的抗菌活性物质不易流失。本发明所述的复合金属胶体抗菌的有机人造石,具有耐热性好、广谱抗菌、缓释性优良和采购成本低等特点,具有更加良好的成本优势。(The invention discloses an organic artificial stone with composite metal colloid antibacterial property and a preparation method of an antibacterial agent of the organic artificial stone. The antibacterial adhesive comprises an antibacterial adhesive solution, wherein the antibacterial adhesive solution comprises a composite metal colloid antibacterial agent, and the composite metal colloid antibacterial agent comprises zirconium hydroxy phosphate micro powder, silver atoms, copper atoms and nano titanium dioxide; wherein the silver atom and copper atom colloid are adsorbed on the surface micropores of the nano titanium dioxide, and the silver atom, copper atom and nano titanium dioxide colloid are adsorbed on the surface of the zirconium hydroxy phosphate micro powder; the silver atoms are used as an activating agent, the copper atoms are used as an antibacterial agent to be activated, and the nano titanium dioxide is used as an ultraviolet sterilizing body. The antibacterial active substance contained in the composite metal colloid antibacterial agent is not easy to run off. The composite metal colloid antibacterial organic artificial stone has the characteristics of good heat resistance, broad-spectrum antibacterial property, excellent slow release property, low purchase cost and the like, and has better cost advantage.)

1. The composite metal colloid antibacterial organic artificial stone is characterized by comprising an antibacterial bonding solution, wherein the antibacterial bonding solution comprises a composite metal colloid antibacterial agent which comprises zirconium hydroxy phosphate micro powder, silver atoms, copper atoms and nano titanium dioxide; wherein the silver atom and copper atom colloid are adsorbed on the surface micropores of the nano titanium dioxide, and the silver atom, copper atom and nano titanium dioxide colloid are adsorbed on the surface of the zirconium hydroxy phosphate micro powder; the silver atoms are used as an activating agent, the copper atoms are used as an antibacterial agent to be activated, and the nano titanium dioxide is used as an ultraviolet sterilizing body.

2. An organic artificial stone according to claim 1, wherein the composite metal colloid antibacterial agent accounts for 1 to 3% of the total mass of the artificial stone; the raw material components of the antibacterial binding liquid also comprise water and a coupling agent, wherein the coupling agent is a titanium phosphate type surfactant; the antibacterial bonding liquid is a pre-prepared mixed liquid before being added into the organic artificial stone.

3. The composite metal colloid antibacterial organic artificial stone according to claim 2, wherein the composite metal colloid antibacterial agent further comprises zinc oxide, the zinc oxide is a stabilizer, the zinc oxide is a colloid adsorbed on zirconium hydroxy phosphate micropowder, and the zinc oxide is used for delaying silver oxide in an alkaline environment from being alkalized, so that silver oxide is prevented from being converted into silver hydroxide firstly and being separated out, and copper atoms cannot be converted into copper ions.

4. The composite metal colloid antibacterial organic artificial stone according to claim 3, wherein the molar contents of copper atoms, zinc oxide and silver atoms adsorbed to the zirconium hydroxyphosphate fine powder and the nano titanium dioxide are all decreased in order.

5. The composite metal colloid antibacterial organic artificial stone according to claim 3, wherein the molar content ratio of the copper atoms, the nano titanium dioxide, the zinc oxide and the silver atoms adsorbed by the zirconium hydroxyphosphate micropowder is 4:2:2: 1.

6. The method for preparing the antibacterial agent is characterized in that the organic artificial stone for antibacterial composite metal colloid of any one of claims 1 to 5 comprises the following specific steps:

s1) adding silver nitrate, nano titanium dioxide, copper nitrate and zinc oxide into water, and stirring and mixing uniformly to obtain a silver-copper-zinc nitric acid solution;

s2) adding zirconium sodium hydroxy phosphate micro powder into silver-copper-zinc-nitric acid solution, adjusting the pH value by using dilute nitric acid and dilute sodium hydroxide solution, keeping the temperature of water bath constant, and fully and uniformly stirring to obtain zirconium hydroxy phosphate micro powder adsorption solution;

s3) putting the zirconium hydroxy phosphate micro powder adsorption solution into an oven for drying to prepare zirconium hydroxy phosphate micro powder adsorption dry powder;

s4) conveying the zirconium hydroxy phosphate micro powder adsorption dry powder into a reduction sintering furnace for heating and roasting;

s5) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain zirconium hydroxy phosphate micro powder adsorption baking powder;

s6) sieving the zirconium hydroxy phosphate micro powder adsorption baking powder to obtain the composite metal colloid antibacterial agent.

7. The method of claim 6, wherein in step S1, the silver-copper-zinc-nitric acid solution contains copper nitrate, nano titanium dioxide, zinc oxide, silver nitrate and water at a mixing molar ratio of 2.5:1:1:0.5: 20; in the step S2, the molar ratio of the silver-copper-zinc nitrate solution to the zirconium hydroxy phosphate micro powder is 1:4, the water bath temperature is 50 ℃, the pH value is 3-4, and the stirring time is 3-4 hours.

8. The method for preparing an antibacterial agent according to claim 6, wherein in the step 3, the temperature of the drying is 100-120 ℃; in the step S4, the roasting temperature is 500-600 ℃, and the roasting time is 3-4 hours.

9. The method for producing an antibacterial agent according to claim 6, wherein in said step S5, the pressure of adding said carbon monoxide is 0.1 to 0.15MPa, and the time of said reduction reaction is 0.8 to 1 hour; in the step S6, the mesh size of the sieved mesh is 400 mesh.

Technical Field

The invention relates to the technical field of antibacterial agents and artificial stones, in particular to an organic artificial stone with antibacterial composite metal colloid and a preparation method of the antibacterial agent.

Background

The surface of the sodium zirconium hydroxyphosphate has a porous structure, a large specific surface area, strong adsorption capacity, good chemical stability and high temperature resistance, and has good binding force with the antibacterial metal ions adsorbed in the gaps, so that the slow release effect of the antibacterial metal ions can be improved. The sodium zirconium hydroxy phosphate structure has compatibility with various metal ions and can adsorb various metal ions simultaneously.

Disclosure of Invention

The invention provides a composite metal colloid antibacterial organic artificial stone and a preparation method of an antibacterial agent thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

an antibacterial organic artificial stone with composite metal colloid comprises an antibacterial bonding solution, wherein the antibacterial bonding solution comprises a composite metal colloid antibacterial agent which comprises zirconium hydroxy phosphate micro powder, silver atoms, copper atoms and nano titanium dioxide; wherein the silver atom and copper atom colloid are adsorbed on the surface micropores of the nano titanium dioxide, and the silver atom, copper atom and nano titanium dioxide colloid are adsorbed on the surface of the zirconium hydroxy phosphate micro powder; the silver atoms are used as an activating agent, the copper atoms are used as an antibacterial agent to be activated, and the nano titanium dioxide is used as an ultraviolet sterilizing body.

Preferably, the composite metal colloid antibacterial agent accounts for 1-3% of the total mass of the organic artificial stone; the raw material components of the antibacterial binding liquid also comprise water and a coupling agent, wherein the coupling agent is a titanium phosphate type surfactant; the antibacterial bonding liquid is a pre-prepared mixed liquid before being added into the organic artificial stone.

Preferably, the composite metal colloid antibacterial agent further comprises zinc oxide, the zinc oxide is a stabilizer, the zinc oxide is a colloid adsorbed on the zirconium hydroxy phosphate micro powder, and the zinc oxide is used for delaying silver oxide from being alkalized in an alkaline environment, so that the problem that the silver oxide is firstly converted into silver hydroxide to be separated out, and copper atoms cannot be converted into copper ions is avoided.

Preferably, the molar contents of copper atoms, zinc oxide and silver atoms adsorbed on the zirconium hydroxy phosphate micro powder and the nano titanium dioxide are all reduced in sequence.

Preferably, the molar content ratio of the copper atoms, the nano titanium dioxide, the zinc oxide and the silver atoms adsorbed by the zirconium hydroxy phosphate micro powder is 4:2:2: 1.

Further, the invention also provides a preparation method of the antibacterial agent, which is used for the organic artificial stone with the antibacterial composite metal colloid, and comprises the following specific steps:

s1) adding silver nitrate, nano titanium dioxide, copper nitrate and zinc oxide into water, and stirring and mixing uniformly to obtain a silver-copper-zinc nitric acid solution;

s2) adding zirconium sodium hydroxy phosphate micro powder into silver-copper-zinc-nitric acid solution, adjusting the pH value by using dilute nitric acid and dilute sodium hydroxide solution, keeping the temperature of water bath constant, and fully and uniformly stirring to obtain zirconium hydroxy phosphate micro powder adsorption solution;

s3) putting the zirconium hydroxy phosphate micro powder adsorption solution into an oven for drying to prepare zirconium hydroxy phosphate micro powder adsorption dry powder;

s4) conveying the zirconium hydroxy phosphate micro powder adsorption dry powder into a reduction sintering furnace for heating and roasting;

s5) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain zirconium hydroxy phosphate micro powder adsorption baking powder;

s6) sieving the zirconium hydroxy phosphate micro powder adsorption baking powder to obtain the composite metal colloid antibacterial agent.

Further, in the step S1, the silver copper zinc nitric acid solution contains copper nitrate, nano titanium dioxide, zinc oxide, silver nitrate and water in a mixing molar ratio of 2.5:1:1:0.5: 20; in the step S2, the molar ratio of the silver-copper-zinc nitrate solution to the zirconium hydroxy phosphate micro powder is 1:4, the water bath temperature is 50 ℃, the pH value is 3-4, and the stirring time is 3-4 hours.

Further, in the step 3, the drying temperature is 100-; in the step S4, the roasting temperature is 500-600 ℃, and the roasting time is 3-4 hours.

Further, in the step S5, the pressure of adding the carbon monoxide is 0.1 to 0.15MPa, and the time of the reduction reaction is 0.8 to 1 hour; in the step S6, the mesh size of the sieved mesh is 400 mesh.

The invention has the beneficial effects that:

the composite metal colloid antibacterial agent of the organic artificial stone comprises zirconium hydroxy phosphate micro powder loaded with silver, copper metal colloid, nano titanium dioxide and zinc oxide, and has the characteristics of good heat resistance, high-efficiency broad-spectrum antibacterial property, excellent slow release property, ultraviolet ray reinforced sterilization and the like. The antibacterial agent prepared by the preparation method of the antibacterial agent has better cost advantage.

The composite metal colloid antibacterial agent disclosed by the invention contains double adsorption carriers and various antibacterial substances, has a good broad-spectrum sterilization effect, is not easy to run off, and is suitable for being used in places with high antibacterial sterilization requirements, especially in the medical and food processing industries.

The nano titanium dioxide, zinc oxide and copper nitrate have wide raw material sources and low purchase cost, so that the composite metal colloid antibacterial agent has better cost advantage and more optimized slow release performance compared with the silver ion-loaded zirconium hydroxyphosphate antibacterial agent in the prior art.

The invention provides the preparation method of the antibacterial agent, and the prepared antibacterial agent containing the double-carrier structure and various antibacterial substances is convenient to store and use.

Detailed Description

The technical solution of the present invention is further described below in specific embodiments.

An antibacterial organic artificial stone with composite metal colloid comprises an antibacterial bonding solution, wherein the antibacterial bonding solution comprises a composite metal colloid antibacterial agent which comprises zirconium hydroxy phosphate micro powder, silver atoms, copper atoms and nano titanium dioxide; wherein the silver atom and copper atom colloid are adsorbed on the surface micropores of the nano titanium dioxide, and the silver atom, copper atom and nano titanium dioxide colloid are adsorbed on the surface of the zirconium hydroxy phosphate micro powder; the silver atoms are used as an activating agent, the copper atoms are used as an antibacterial agent to be activated, and the nano titanium dioxide is used as an ultraviolet sterilizing body.

The antibacterial bonding liquid is used for bonding solid raw materials of the organic artificial stone and is uniformly distributed in the organic artificial stone. Include in the even distribution of composite metal colloid antibacterial agent in the antibiotic bonding liquid in the organic artificial stone, and be bonded in the organic artificial stone, can make the antibiotic effect of organic artificial stone more stable and even.

The solid raw materials of the organic artificial stone comprise quartz stone, marble, granite, feldspar, super quartz stone and colorant.

The composite metal colloid antibacterial organic artificial stone comprises a composite metal colloid antibacterial agent, silver atoms are used as an activating agent, copper atoms are used as an antibacterial agent to be activated, and nano titanium dioxide is used as an ultraviolet sterilization body; the nano titanium dioxide is anatase nano titanium dioxide.

The zirconium hydroxy phosphate micro powder is prepared from sodium zirconium hydroxy phosphate, has hydrophilic groups and has good compatibility with aqueous solution. The sodium zirconium hydroxy phosphate has large specific surface area and high surface energy, can be used as an ideal carrier of the bactericidal and antibacterial metal ions, can store a large amount of bactericidal and antibacterial metal colloid, can reduce the loss of the bactericidal and antibacterial metal colloid, and improves the release concentration and the sustained release capacity of the bactericidal and antibacterial metal ions.

The silver-copper metal colloid loaded on the zirconium phosphate hydroxyl micropowder and the nano titanium dioxide can release active silver atoms and copper atoms, and the metal atom colloid is less prone to being damped and lost than a metal ion colloid, so that the slow-release effective period of the antibacterial substance can be prolonged.

When silver atoms are in a humid environment containing oxygen, such as contact with water, acid or alkaline solution, the silver atoms are oxidized into silver ions; when silver atom, silver ion and copper atom exist simultaneously, the electrode potential of silver ion/silver is 0.80 volt, the electrode potential of copper ion/copper is 0.34 volt, and due to the potential difference of electrode potential, the silver ion in the metal colloid can oxidize the copper atom in the colloid into colloid copper ion, and the silver ion is reduced into silver atom, and the chemical reaction formula is 2Ag⁺+Cu＝2Ag+Cu⁺⁺The potential difference is released E⁰＝ψ(Ag⁺/Ag-ψCu⁺⁺0.80-0.34-0.46 volt, and the copper atom in colloid is converted into Cu with bactericidal and antibacterial activity⁺⁺Ions.

When in oxygen-containing humid environment, silver atoms are oxidized into silver ions, copper atoms in the silver ion oxidized colloid are colloid copper ions and are copper ions with antibacterial activity, and the antibacterial activity of the composite metal colloid antibacterial agent is activated. The dried composite metal colloid antibacterial agent has good stability, and antibacterial active substances are not easy to run off.

The nano titanium dioxide selected by the invention is anatase type nano titanium dioxide which is a white powdery substance, has stable chemical property, strong photocatalytic oxidation reduction capability, high chemical stability and no toxicity, can be excited by visible light below 380nm, has strong oxidation effect under the action of sunlight or ultraviolet light, and can oxidize and decompose harmful organic matters such as formaldehyde, methylamine, benzene, xylene, ammonia, TVOC and the like, pollutant odor, bacteria and the like into harmless carbon dioxide and water. Has the characteristics of bacteriostasis, sterilization, disinfection, pollutant removal, hydrophilicity, self-cleaning property and the like, and has the characteristics of low price, no toxicity, and good acid-base chemical stability.

The nano titanium dioxide has good bactericidal effect under the irradiation of ultraviolet rays, has catalytic effect on the oxidative decomposition of organic pollutants, and has good adsorption performance. Is very suitable for the daily working environment needing ultraviolet sterilization, can improve the sterilization and decontamination effects, and can assist the adsorbed antibacterial substances to improve the broad-spectrum sterilization efficiency.

The composite metal colloid antibacterial agent disclosed by the invention contains double adsorption carriers and various antibacterial substances, has a good broad-spectrum sterilization effect, is not easy to run off, and is suitable for being used in places with high antibacterial sterilization requirements, especially in the medical and food processing industries.

Preferably, the composite metal colloid antibacterial agent accounts for 1-3% of the total mass of the organic artificial stone; the raw material components of the antibacterial binding liquid also comprise water and a coupling agent, wherein the coupling agent is a titanium phosphate type surfactant; the antibacterial bonding liquid is a pre-prepared mixed liquid before being added into the organic artificial stone.

The organic artificial stone containing 1-3% of the composite metal colloid antibacterial agent can meet the requirements of JC/T897-2014 'antibacterial ceramic product antibacterial performance' standard through detection on antibacterial performance and antibacterial durability. The content of the composite metal colloid antibacterial agent contained in the organic artificial stone is lower than 1%, and the antibacterial performance index does not reach the standard; the content of the composite metal colloid antibacterial agent contained in the organic artificial stone is higher than 3%, the antibacterial performance is excessive, and resources are wasted.

Because the main raw materials of prior art's organic rostone are mostly cement system material, and basicity is higher, contains water with the raw materials antibiotic bonding solution disposes, adds the prefabricated material of organic rostone again, can avoid the basicity of the cement system material in the organic rostone to destroy silver ion that antibiotic bonding solution contains avoids silver ion to become silver hydroxide, leads to the conversion rate reduction of copper atom conversion copper ion, and influences the antibacterial property of the organic rostone that composite metal colloid antiseptic prepared.

The raw materials of the antibacterial binding solution comprise a coupling agent which is a titanium phosphate type surfactant, the titanium phosphate type surfactant has good compatibility with zirconium hydroxy phosphate micro powder and aqueous solution, the compatibility of the composite metal colloid antibacterial agent and inorganic solid raw materials contained in the organic artificial stone can be improved, and the stability of the composite metal colloid antibacterial agent in the organic artificial stone is improved.

Preferably, the composite metal colloid antibacterial agent further comprises zinc oxide, the zinc oxide is a stabilizer, the zinc oxide is a colloid adsorbed on the zirconium hydroxy phosphate micro powder, and the zinc oxide is used for delaying silver oxide from being alkalized in an alkaline environment, so that the problem that the silver oxide is firstly converted into silver hydroxide to be separated out, and copper atoms cannot be converted into copper ions is avoided.

The zinc oxide is an antibacterial agent with a good antibacterial effect, has photosensitive bactericidal performance, is wide in raw material source and low in purchase cost, and has superior cost advantage compared with silver nitrate powder because silver nitrate is a raw material of silver atoms.

The silver oxide colloid is adsorbed on the composite metal colloid antibacterial agent, has better stability and is not easy to lose, the composite metal colloid antibacterial agent contains various active antibacterial substances, has wider product application range and more comprehensive antibacterial effect, and has better finished product advantages while improving the slow release performance.

The zinc oxide adsorbed on the composite metal colloid antibacterial agent is used for protecting silver oxide from being alkalized in an alkaline environment and preventing the silver oxide from being separated out by being converted into silver hydroxide, so that the conversion rate of copper atoms into copper ions is reduced, and the antibacterial performance of the composite metal colloid antibacterial agent is reduced. Only after the zinc oxide is consumed by the reaction, the silver oxide is alkalized and converted into silver hydroxide to be separated out.

Therefore, the antibacterial organic artificial stone with the composite metal colloid has the performance of avoiding silver precipitation and discoloration, and the product can have better color or transparent effect.

The zinc oxide has good activity, can improve the adverse effect of precipitation under the alkaline environment of silver ions, and has the following chemical reaction mechanism.

Silver ions react with basic groups in alkaline environment to generate silver hydroxide precipitate

Ag⁺+OH^-AgOH ↓ (white)

Unstable decomposition of silver hydroxide precipitate to silver oxide precipitate

2AgOH＝Ag₂O ↓ (dark brown) + H₂O

When zinc oxide and silver oxide coexist, the chemical reaction activity of the zinc oxide under the alkaline environment is higher than that of the silver oxide, and the zinc oxide firstly reacts with basic groups to delay and prevent the precipitation of the silver oxide.

ZnO++2OH^-＝Zn(OH)₂↓ (white)

The zinc oxide is used as a stabilizer of silver ions, so that the stability of the antibacterial performance of the composite metal colloid antibacterial agent can be improved, and the alkaline application range of the composite metal colloid antibacterial agent can be widened by increasing the using amount and proportion of the zinc oxide.

Preferably, the molar contents of copper atoms, zinc oxide and silver atoms adsorbed on the zirconium hydroxy phosphate micro powder and the nano titanium dioxide are all reduced in sequence.

The composite metal colloid antibacterial agent contains silver atoms in oxygen-containing humid environment, and can effectively convert copper atoms into copper ions. Under the condition of keeping the effect of converting copper ions of silver atoms, the use amount of silver nitrate in the raw materials is reduced, and the use amounts of copper nitrate and zinc oxide are increased, so that the cost advantage of the composite metal colloid antibacterial agent can be effectively improved, and the composite metal colloid antibacterial agent is more environment-friendly.

Preferably, the molar content ratio of the copper atoms, the nano titanium dioxide, the zinc oxide and the silver atoms adsorbed by the zirconium hydroxy phosphate micro powder is 4:2:2: 1.

The molar content ratio of copper atoms, nano titanium dioxide, zinc oxide and silver atoms adsorbed by the zirconium hydroxy phosphate micro powder is 4:2:2:1, so that the cost performance is better, the composite metal colloid antibacterial agent has a good antibacterial effect, and a better cost advantage can be obtained.

The nano titanium dioxide can have a bactericidal effect only under the irradiation of near ultraviolet rays and low-frequency visible light, and simultaneously serves as an adsorption carrier of part of antibacterial metal ions, so that the molar content ratio of the nano titanium dioxide in the total mass of copper atoms, the nano titanium dioxide, zinc oxide and silver atoms is not more than 25%, otherwise, the number of the copper atoms, the nano titanium dioxide, the zinc oxide and the silver atoms adsorbed on the nano titanium dioxide is too large, and the adsorption rate of the copper atoms, the zinc oxide and the silver atoms in the zirconium hydroxy phosphate micro powder is relatively low. And the molar content ratio of the nano titanium dioxide in the copper atoms, the nano titanium dioxide, the zinc oxide and the silver atoms is lower than 20%, so that the sterilizing rate under the ultraviolet irradiation is low, and the method is not suitable for the requirements of high-standard use places.

The molar content ratio of the zinc oxide to the silver atoms is 2:1, the probability that the silver oxide is firstly alkalized can be reduced, the conversion rate of converting the copper atoms adsorbed by the zirconium hydroxy phosphate micro powder into copper ions can be improved, and the stability of the antibacterial performance of the composite metal colloid antibacterial agent can be ensured.

Further, the invention also provides a preparation method of the antibacterial agent, which is used for the organic artificial stone with the antibacterial composite metal colloid, and comprises the following specific steps:

s1) adding silver nitrate, nano titanium dioxide, copper nitrate and zinc oxide into water, and stirring and mixing uniformly to obtain a silver-copper-zinc nitric acid solution;

s2) adding zirconium sodium hydroxy phosphate micro powder into silver-copper-zinc-nitric acid solution, adjusting the pH value by using dilute nitric acid and dilute sodium hydroxide solution, keeping the temperature of water bath constant, and fully and uniformly stirring to obtain zirconium hydroxy phosphate micro powder adsorption solution;

s3) putting the zirconium hydroxy phosphate micro powder adsorption solution into an oven for drying to prepare zirconium hydroxy phosphate micro powder adsorption dry powder;

s4) conveying the zirconium hydroxy phosphate micro powder adsorption dry powder into a reduction sintering furnace for heating and roasting;

s5) adding carbon monoxide into a constant-temperature reduction sintering furnace, and carrying out reduction reaction to obtain zirconium hydroxy phosphate micro powder adsorption baking powder;

s6) sieving the zirconium hydroxy phosphate micro powder adsorption baking powder to obtain the composite metal colloid antibacterial agent.

The preparation method of the antibacterial agent comprises the steps of dipping the zirconium hydroxy phosphate micro powder in an aqueous solution of silver nitrate, nano titanium dioxide, copper nitrate and zinc oxide, wherein the nano titanium dioxide is insoluble in a nitric acid solution, and when the concentrations of the silver nitrate, the copper nitrate and the zinc oxide are higher and higher than the concentration of the nano titanium dioxide, part of Ag in the nano titanium dioxide is adsorbed on the surface of the nano titanium dioxide⁺、Cu⁺⁺And Zn⁺⁺Ions, remainder Ag⁺、Cu⁺⁺And Zn⁺⁺Ions are adsorbed on the zirconium hydroxy phosphate micro powder, and the zirconium hydroxy phosphate micro powder with larger specific surface area adsorbs the nano titanium dioxide on the surface of the zirconium hydroxy phosphate micro powder to form a double composite carrier. Therefore, the composite metal colloid antibacterial agent has more efficient and broad-spectrum antibacterial performance.

Because of the high temperature stability of the sodium zirconium hydroxy phosphate, after the antibacterial metal ion salt solution is adsorbed at normal temperature, the antibacterial metal ions are oxidized into oxides by baking at high temperature, so that the binding force of the antibacterial metal ions in the sodium zirconium hydroxy phosphate is enhanced, the metal ions are further reduced into metal atoms, the dissociated antibacterial metal atoms are controlled, the antibacterial metal elements in the carrier are ensured to generate good slow release effect, and the long-term antibacterial effect is achieved.

The metal ions adsorbed on the zirconium hydroxy phosphate micro powder and the nano titanium dioxide are Ag⁺、Cu⁺⁺And Zn⁺⁺Ion, nano titanium dioxide is adsorbed on zirconium hydroxy phosphate micro powder, and then the zirconium hydroxy phosphate micro powder is baked at high temperature after being dried, so that Ag is obtained⁺、Cu⁺⁺And Zn⁺⁺Ionic conversion to silver oxide, copper oxide and oxidationAnd zinc, and then reducing silver oxide and copper oxide into silver atom colloid and copper atom colloid by using carbon monoxide under high-temperature vacuum, wherein nano titanium dioxide and zinc oxide can not be reduced and still can be adsorbed on the surface of the zirconium hydroxy phosphate micro powder in a colloid form, and metal colloid containing silver and copper atoms and zinc oxide colloid are adsorbed on the surface of the zirconium hydroxy phosphate micro powder to form the zirconium hydroxy phosphate micro powder with antibacterial activity.

Common zinc oxide powder is dissolved into Zn⁺⁺The ions are oxidized again to oxidize the zinc, and the formed colloid is adsorbed on the zinc oxide on the surface of the zirconium hydroxy phosphate micro powder, so the antibacterial agent has broad-spectrum antibacterial performance and good antibacterial effect on candida albicans.

The nano titanium dioxide is a white powdery substance, has stable chemical properties, strong photocatalytic oxidation reduction capability, high chemical stability and no toxicity, can be excited by visible light below 380nm, has extremely strong oxidation effect under the action of sunlight or ultraviolet light, and can oxidize and decompose harmful organic matters such as formaldehyde, methylamine, benzene, xylene, ammonia, TVOC and the like, pollutant odor, bacteria and the like into harmless carbon dioxide and water. Has the characteristics of bacteriostasis, sterilization, disinfection, pollutant removal, hydrophilicity, self-cleaning property and the like, and has the characteristics of low price, no toxicity and good chemical stability.

The nano titanium dioxide has good bactericidal effect under the irradiation of ultraviolet rays, has catalytic effect on the oxidative decomposition of organic pollutants, and also has better adsorption performance. The ultraviolet sterilization and decontamination agent is very suitable for the daily working environment requiring ultraviolet sterilization, can provide sterilization and decontamination effects, and can assist the adsorbed antibacterial substances to improve the broad-spectrum sterilization efficiency.

The nano titanium dioxide can adopt nano titanium dioxide, the zinc oxide adopts zinc oxide powder, the copper oxide adopts copper nitrate powder, the raw material source is wide, and the purchase cost is low.

Therefore, the composite metal colloid antibacterial agent is zirconium hydroxy phosphate micro powder loaded with silver atoms, copper atoms, nano titanium dioxide and zinc oxide, and has the characteristics of good heat resistance, high-efficiency broad-spectrum antibacterial property, excellent slow release property, ultraviolet ray reinforced sterilization and the like. Compared with the silver-loaded zirconium hydroxyphosphate antibacterial agent, the composite metal colloid antibacterial agent has better cost advantage.

Further, in the step S1, the silver copper zinc nitric acid solution contains copper nitrate, nano titanium dioxide, zinc oxide, silver nitrate and water in a mixing molar ratio of 2.5:1:1:0.5: 20; in the step S2, the molar ratio of the silver-copper-zinc nitrate solution to the zirconium hydroxy phosphate micro powder is 1:4, the water bath temperature is 50 ℃, the pH value is 3-4, and the stirring time is 3-4 hours.

The molar ratio of copper nitrate to nano titanium dioxide to zinc oxide to silver nitrate to water is 2.5:1:1:0.5:20, the total content of silver, copper and zinc ions and the nano titanium dioxide antibacterial active substance is high, and the adsorption efficiency of zirconium hydroxy phosphate can be improved.

The ratio of the silver-copper-zinc nitrate solution to the zirconium hydroxy phosphate micro powder is 1:4, the concentration of the contained antibacterial active substance is high, and the composite metal colloid antibacterial agent has a good antibacterial effect and is convenient to store and use.

The water bath temperature is 50 ℃, the pH value is 3-4, the stirring time is-4 hours, the dissolution and adsorption efficiency of silver ions can be improved in an acid environment of 50 ℃ for 3-4 hours, and the strength of the silver ions adsorbed on zirconium hydroxy phosphate micro powder is improved.

Further, in the step 3, the drying temperature is 100-; in the step S4, the roasting temperature is 500-600 ℃, and the roasting time is 3-4 hours.

The drying temperature is not lower than 100 ℃, and the zirconium hydroxy phosphate micro powder can be fully dried to adsorb the water contained in the solution.

Silver nitrate and copper nitrate are roasted at high temperature to form silver oxide and copper oxide, and then the silver oxide and the copper oxide are reduced by carbon monoxide at high temperature under vacuum to form metal colloid, and the metal colloid of silver and copper is gathered on the surface of zirconium hydroxy phosphate micro powder to be condensed into zirconium hydroxy phosphate micro powder with antibacterial activity.

The decomposition temperature of the silver nitrate is 440 ℃, the silver nitrate can be completely decomposed and oxidized into silver oxide by roasting at the temperature of more than 500 ℃, the decomposition temperature of the copper nitrate is lower than that of the silver nitrate, and the decomposition and oxidation of the copper nitrate are more complete. The high-temperature treatment can also increase the adsorbed strength of silver ions and prolong the slow-release effective period of the antibacterial agent, the effect is better at the temperature of 500-600 ℃, and the activity of the silver ions can be destroyed when the temperature exceeds 600 ℃, so that the proportion of the silver ions to be separated out and reduced is influenced. Therefore, the composite metal colloid antibacterial agent has relatively stable antibacterial metal precipitation performance and silver discoloration resistance.

Further, in the step S5, the pressure of adding the carbon monoxide is 0.1 to 0.15MPa, and the time of the reduction reaction is 0.8 to 1 hour; in the step S6, the mesh size of the sieved mesh is 400 mesh.

Has the advantages that: when the roasting is carried out at 500 ℃, the reduction effective rate of the silver oxide and the copper oxide can be reduced when the pressure of the added carbon monoxide is lower than 0.1MPa, and resources are wasted when the pressure is higher than 0.15 MPa. The roasting temperature is 500-600 ℃, the temperature is higher than 440 ℃ and is maintained for 0.8-1 hour, so that the reduction rate of the silver oxide and the copper oxide reduced into silver-copper colloid can be improved. The reducing gas can also adopt hydrogen, and carbon monoxide is more convenient and lower in cost than hydrogen, so that the method has better economic benefit.

The smaller the particle size of the zirconium hydroxy phosphate micro powder is, the larger the surface area ratio of the zirconium hydroxy phosphate micro powder is, the higher the activity of the loaded silver-copper colloid is, the particle size of the conventional zirconium hydroxy phosphate micro powder is 325 meshes, and the bonded composite metal colloid antibacterial agent with overlarge particle size can be removed by filtering with a 400-mesh filter sieve, so that the bad appearance of particles with uneven distribution is avoided when the zirconium hydroxy phosphate micro powder is used.