阅读说明：本技术 抗菌剂的制备方法、其抗菌剂及使用其的抗菌人造石 (Method for preparing antibacterial agent, antibacterial agent and antibacterial artificial stone using same ) 是由 高忠麟 舒诚 于 2020-08-12 设计创作，主要内容包括：本发明公开了抗菌剂的制备方法、其抗菌剂及使用其的抗菌人造石,一种抗菌剂的制备方法,包括以下步骤：A、将玻璃原料混合后,形成玻璃混合料；B、将玻璃混合料熔制出可以溶出抗菌金属离子的硼铝磷酸盐玻璃；C、将硼铝磷酸盐玻璃加入球磨机进行球磨,形成抗菌剂。本技术方案提出的一种抗菌剂的制备方法,其抗菌效果强,且操作简单,方便制备。进而提出一种利用上述抗菌剂的制备方法制备的抗菌剂,其抗菌效果强,且稳定性高、安全环保性好、成本低。还提出一种使用上述抗菌剂的抗菌人造石,其抗菌率可达到88％或以上。(The invention discloses a preparation method of an antibacterial agent, the antibacterial agent and an antibacterial artificial stone using the antibacterial agent, and the preparation method of the antibacterial agent comprises the following steps: A. mixing glass raw materials to form a glass mixture; B. melting the glass mixture to prepare boron-aluminum phosphate glass capable of dissolving out antibacterial metal ions; C. adding the boron-aluminum phosphate glass into a ball mill for ball milling to form the antibacterial agent. The preparation method of the antibacterial agent provided by the technical scheme has the advantages of strong antibacterial effect, simple operation and convenient preparation. The antibacterial agent prepared by the preparation method of the antibacterial agent has the advantages of strong antibacterial effect, high stability, good safety and environmental protection and low cost. Also provided is an antibacterial artificial stone using the antibacterial agent, the antibacterial rate of which can reach 88% or more.)

1. A method for preparing an antibacterial agent, comprising the steps of:

A. mixing glass raw materials to form a glass mixture;

B. melting the glass mixture to prepare boron-aluminum phosphate glass capable of dissolving out antibacterial metal ions; wherein the chemical composition of the boron-aluminum phosphate glass comprises P according to the mass percentage₂O₅60～80％、B₂O₃5～25％、Al₂O₃3～10％、CaO 5～8％、K₂0 5～10％、CuO 1～5％、Ag₂1-2% of O and 0-10% of ZnO;

C. adding the boron-aluminum phosphate glass into a ball mill for ball milling to form the antibacterial agent.

2. The method for producing an antibacterial agent according to claim 1, wherein: step E is also included after step C;

E. activating the antibacterial agent by using an activating agent, and then putting the activated antibacterial agent into an oven for drying treatment.

3. The method for producing an antibacterial agent according to claim 2, wherein: the activator is isopropyl tri (dioctyl pyrophosphato acyloxy) titanate.

4. The method for producing an antibacterial agent according to claim 1, wherein: in the step of ball milling, the fineness of the antibacterial agent is less than or equal to 100 meshes.

5. The method for producing an antibacterial agent according to claim 1, wherein: in the melting step, the melting temperature of the boron-aluminum phosphate glass is 1300-1350 ℃.

6. An antimicrobial agent characterized by: the antibacterial agent is prepared by the preparation method of any one of the antibacterial agents of claims 1 to 5.

7. An antibacterial artificial stone is characterized in that: the raw materials thereof comprise the antibacterial agent of claim 6;

the antibacterial artificial stone comprises the following raw materials in parts by weight: 7-10 parts of an antibacterial agent, 71-88 parts of an artificial stone filler and 14 parts of an inorganic binder.

8. An antimicrobial synthetic stone according to claim 7, wherein: the artificial stone filler is any one of quartz stone filler, marble filler or feldspar filler.

9. An antimicrobial synthetic stone according to claim 7, wherein: the inorganic binder comprises the following raw materials in parts by weight: 15-20 parts of white portland cement, 5-10 parts of polycarboxyl butylbenzene emulsion, 0.5-2 parts of polycarboxylic acid water reducing agent and 0.5-1 part of tributyl phosphate.

10. An antimicrobial synthetic stone according to claim 9, wherein: the strength of the white Portland cement is 52.5-62.5 MPa, and the solid content of the polycarboxyl styrene-butadiene emulsion is not less than 50%.

Technical Field

The invention relates to the field of artificial stones, in particular to a preparation method of an antibacterial agent, the antibacterial agent and an antibacterial artificial stone using the antibacterial agent.

Background

With the technical progress of stone materials, consumers have increasingly high requirements on the influence of stone materials on the home environment, and particularly, stone materials with antibacterial and antibacterial functions have become very popular abroad and have a basic requirement on stone materials.

In the past, the stone generally uses an antibacterial agent containing silver ions, and metal silver belongs to precious rare metals, so that the price is high and the cost is high. So that it is the most important obstacle to the popularization of the stone with antibacterial function. In addition, silver ions darken the color of the stone, which limits its application in some respects. At present, the antibacterial agent comprises an organic antibacterial agent and an inorganic antibacterial agent, wherein the organic antibacterial agent has a good antibacterial effect, but the effective time of the organic antibacterial agent is short in duration and easy to lose effectiveness. The inorganic materials widely used are simple substance nanometer metal powder, such as nanometer silver, nanometer zinc oxide, nanometer titanium dioxide, etc., and the inorganic materials have high price and few sources, and are difficult to be widely popularized in stone materials.

Disclosure of Invention

The invention aims to provide a preparation method of an antibacterial agent, which has strong antibacterial effect, simple operation and convenient preparation and overcomes the defects in the prior art.

The invention also aims to provide the antibacterial agent prepared by the preparation method of the antibacterial agent, which has the advantages of strong antibacterial effect, high stability, good safety and environmental protection and low cost.

Another object of the present invention is to provide an artificial antibacterial stone using the above antibacterial agent, which has an antibacterial rate of 88% or more.

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

a method for preparing an antibacterial agent comprising the steps of:

A. mixing glass raw materials to form a glass mixture;

B. melting the glass mixture to prepare boron-aluminum phosphate glass capable of dissolving out antibacterial metal ions; the boroaluminophosphate glass comprises, by mass, 560-80% of P2O, 35-25% of B2O, 33-10% of Al2O, 5-8% of CaO, 205-10% of K, 1-5% of CuO, 1-2% of Ag2O and 0-10% of ZnO;

C. adding the boron-aluminum phosphate glass into a ball mill for ball milling to form the antibacterial agent.

Preferably, step C is followed by step E;

E. activating the antibacterial agent by using an activating agent, and then putting the activated antibacterial agent into an oven for drying treatment.

Preferably, the activator is isopropyl tris (dioctyl pyrophosphato acyloxy) titanate.

Preferably, in the step of ball milling, the fineness of the antibacterial agent is less than or equal to 100 meshes.

Preferably, in the melting step, the melting temperature of the boroaluminophosphate glass is 1300-1350 ℃.

An antibacterial agent is prepared by the preparation method of the antibacterial agent.

An antibacterial artificial stone, which comprises the antibacterial agent;

the antibacterial artificial stone comprises the following raw materials in parts by weight: 7-10 parts of an antibacterial agent, 71-88 parts of an artificial stone filler and 14 parts of an inorganic binder.

Preferably, the artificial stone filler is any one of quartz, marble or feldspar.

Preferably, the inorganic binder consists of the following raw material components in parts by mass: 15-20 parts of white portland cement, 5-10 parts of polycarboxyl butylbenzene emulsion, 0.5-2 parts of polycarboxylic acid water reducing agent and 0.5-1 part of tributyl phosphate.

Preferably, the strength of the white portland cement is 52.5-62.5 MPa, and the solid content of the polycarboxyl styrene-butadiene emulsion is not less than 50%.

The invention has the beneficial effects that: the preparation method of the antibacterial agent provided by the technical scheme has the advantages of strong antibacterial effect, simple operation and convenient preparation. The antibacterial agent prepared by the preparation method of the antibacterial agent has the advantages of strong antibacterial effect, high stability, good safety and environmental protection and low cost. Also provided is an antibacterial artificial stone using the antibacterial agent, the antibacterial rate of which can reach 88% or more.

Detailed Description

A method for preparing an antibacterial agent comprising the steps of:

A. mixing glass raw materials to form a glass mixture;

B. melting the glass mixture to prepare boron-aluminum phosphate glass capable of dissolving out antibacterial metal ions; wherein the chemical composition of the boron-aluminum phosphate glass comprises P according to the mass percentage₂O₅60～80％、B₂O₃5～25％、Al₂O₃3～10％、CaO5～8％、K₂05～10％、CuO1～5％、Ag₂O1-2% and ZnO 0-10%;

C. adding the boron-aluminum phosphate glass into a ball mill for ball milling to form the antibacterial agent.

In the past, the stone generally uses an antibacterial agent containing silver ions, and metal silver belongs to precious rare metals, so that the price is high and the cost is high. So that it is the most important obstacle to the popularization of the stone with antibacterial function. In addition, silver ions darken the color of the stone, which limits its application in some respects. At present, the antibacterial agent comprises an organic antibacterial agent and an inorganic antibacterial agent, wherein the organic antibacterial agent has a good antibacterial effect, but the effective time of the organic antibacterial agent is short in duration and easy to lose effectiveness. The inorganic materials widely used are simple substance nanometer metal powder, such as nanometer silver, nanometer zinc oxide, nanometer titanium dioxide, etc., and the inorganic materials have high price and few sources, and are difficult to be widely popularized in stone materials.

In order to solve the problems, the technical scheme provides a preparation method of the antibacterial agent, which comprises three steps, and is simple to operate and convenient to prepare.

The general antibacterial metal ions have strong oxidation effect on bacteria only when in high valence state, thereby achieving the antibacterial effect. The antibacterial metal ions are beneficial to keeping the existence of the high-valence metal ions in the acidic environment, and are not beneficial to the formation of the high-valence metal ions in the alkaline environment. Therefore, the technical scheme selects the boron-aluminum phosphate system glass with stronger acidity as the carrier of the antibacterial metal ions, is favorable for ensuring that the antibacterial metal ions exist in a high valence state, effectively overcomes the adverse effect of an alkaline environment on the high valence state antibacterial metal ions, and ensures the antibacterial activity of the antibacterial metal ions.

Furthermore, the chemical components of the boron-aluminum phosphate glass in the technical scheme comprise P₂O₅60～80％、B₂O₃5～25％、Al₂O₃3～10％、CaO5～8％、K₂05～10％、CuO1～5％、Ag₂O1-2% and ZnO 0-10%. Wherein, P₂O₅And B₂O₃Is a glass forming body, and is beneficial to ensuring the generation of boron aluminum phosphate glass. Al (Al)₂O₃Is an amphoteric oxide, and when the glass contains excessive free oxygen, it can absorb the free oxygen and convert it from non-vitreous alundum to vitreous alundum into glass phase, so as to stabilize vitrification, raise hardness and strengthHowever, when the content is large, the temperature of the molten glass rises and the viscosity increases. K₂O is a glass cosolvent, and is introduced into a boron aluminum phosphate system, so that the temperature and the viscosity of the glass during melting are reduced. CuO and Ag₂O is introduced into the boron-aluminum phosphate system as a source of antibacterial metal ions, and is beneficial to improving the antibacterial effect of the antibacterial agent. ZnO can reduce the viscosity of the glass, and the main purpose of the introduction is to play a role in photosensitive-dissolution antibacterial action, thereby further improving the antibacterial effect of the antibacterial agent.

It should be noted that the boroaluminophosphate glass in the technical scheme can be prepared from conventional glass raw materials, and the boroaluminophosphate glass with the chemical components required in the technical scheme can be obtained by adjusting the types and the proportions of the glass raw materials. Preferably, in an embodiment of the present disclosure, the glass raw material of the boroaluminophosphate glass includes phosphorus pentoxide, boric acid, aluminum hydroxide, calcium carbonate, potassium hydroxide, copper oxide, silver nitrate, and zinc oxide.

More specifically, step C is followed by step E;

E. activating the antibacterial agent by using an activating agent, and then putting the activated antibacterial agent into an oven for drying treatment.

In order to uniformly disperse the antibacterial agent in the raw materials of the artificial stone, reduce the deposition phenomenon of the antibacterial agent and enhance the dispersion and bonding strength of the antibacterial agent in the raw materials of the artificial stone, the technical scheme firstly uses an activating agent to activate the antibacterial agent.

More specifically, the activator is isopropyl tris (dioctyl pyrophosphato acyloxy) titanate.

The isopropyl tri (dioctyl pyrophosphato acyloxy) titanate has the characteristics of strong surface adhesion to the surfaces of nano metal and glass particles, good anti-settling property and good dispersibility, and is used as an activating agent to activate the antibacterial agent, so that the antibacterial agent can be well and uniformly dispersed in the raw materials of the artificial stone, the deposition phenomenon of the antibacterial agent is reduced, and the dispersion and bonding strength of the antibacterial agent in the raw materials of the artificial stone are enhanced.

Further, in the step of ball milling, the fineness of the antibacterial agent is less than or equal to 100 meshes.

In one embodiment of the technical scheme, the fineness of the antibacterial agent is less than or equal to 100 meshes, because the boron-aluminum phosphate glass has poor chemical stability and is easy to dissolve in water, if the fineness of the antibacterial agent is too small, the dissolution rate of the boron-aluminum phosphate glass is easy to be too high, the slow release time of antibacterial metal ions released by a glass body is easy to shorten, and the improvement of the overall antibacterial effect of the antibacterial agent is not facilitated.

Furthermore, in the melting step, the melting temperature of the boroaluminophosphate glass is 1300-1350 ℃.

The melting temperature of the boroaluminophosphate glass is 1300-1350 ℃, so that the antibacterial agent is ensured to slowly release and dissolve out antibacterial metal ions, and the antibacterial artificial stone has a long-acting and continuous antibacterial effect by controlling the precipitation and dissolution speed of the antibacterial metal ions.

An antibacterial agent is prepared by the preparation method of the antibacterial agent.

An antibacterial artificial stone, which comprises the antibacterial agent;

the antibacterial artificial stone comprises the following raw materials in parts by weight: 7-10 parts of an antibacterial agent, 71-88 parts of an artificial stone filler and 14 parts of an inorganic binder.

Furthermore, the technical scheme also provides the antibacterial agent prepared by the preparation method of the antibacterial agent, which has the advantages of strong antibacterial effect, high stability, good safety and environmental protection and low cost.

In the technical scheme, the mixing proportion of the antibacterial agent, the artificial stone filler and the binder is defined as (7-10): (71-88): 14, the artificial stone is beneficial to achieving the best antibacterial effect.

Further, the artificial stone filler is any one of a quartz filler, a marble filler, and a feldspar filler.

The antibacterial agent in the technical scheme is suitable for any one artificial stone filler of quartz stone filler, marble filler or feldspar filler, and has the advantages of wide application range and strong applicability.

Preferably, the quartz stone filler comprises the following raw material components: 60-75 parts of quartz sand, 25-35 parts of quartz powder and 0-5 parts of inorganic metal oxide colorant, wherein the fineness of the quartz sand is less than or equal to 100 meshes, and the fineness of the quartz powder is more than or equal to 325 meshes; the marble filler comprises the following raw material components:

furthermore, the quartz stone filler of the technical scheme is composed of quartz sand with the fineness of less than or equal to 100 meshes and quartz powder with the fineness of more than or equal to 325 meshes in a particle mesh grading manner, so that the quartz stone is favorably ensured to have the smallest gap, the hardness and the strength of the quartz stone are enhanced, the using amount of unsaturated resin is reduced, and the production cost of the quartz stone is reduced. The quartz stone filler also comprises 0-5 parts of inorganic metal oxide colorant, so that the artificial stone can be colored, and the use experience of consumers is improved. More preferably, the inorganic metal oxide colorant is iron oxide.

Preferably, the marble filler comprises the following raw material components: 60-70 parts of marble powder, 60-75 parts of limestone sand, 60-75 parts of calcite sand, 60-75 parts of dolomite sand, 25-40 parts of marble powder, 25-40 parts of limestone powder, 25-40 parts of calcite powder, 25-40 parts of dolomite powder, 0-3 parts of titanium dioxide, 0-4 parts of inorganic metal oxide colorant and 0-2 parts of carbon powder.

Preferably, the feldspar filler comprises the following raw material components: 40-75 parts of feldspar sand, 20-40 parts of marble sand, 0-30 parts of quartz sand, 25-40 parts of feldspar powder, 0-30 parts of marble powder, 0-20 parts of quartz powder, 0-5 parts of titanium dioxide, 0-6 parts of inorganic metal oxide colorant and 0-4 parts of carbon powder.

Further, the inorganic binder comprises the following raw material components in parts by mass: 15-20 parts of white portland cement, 5-10 parts of polycarboxyl butylbenzene emulsion, 0.5-2 parts of polycarboxylic acid water reducing agent and 0.5-1 part of tributyl phosphate.

In the technical scheme of the invention, the antibacterial artificial stone utilizes the inorganic adhesive to resist the antibacterial agent and the artificial stone filler, so that the prepared artificial stone is not easy to age and has low cost.

Specifically, white portland cement serves as both the inorganic binder and the solid filler in the raw materials of the artificial stone, so that the binding power of the inorganic binder can be effectively improved, the forming of the antibacterial artificial stone is ensured, and the hardness of the antibacterial artificial stone is improved. In the polycarboxyl styrene-butadiene emulsion, the polarity of the latex is increased due to the introduction of carboxylic acid, so that the polycarboxyl styrene-butadiene emulsion is introduced into the inorganic binder, the improvement of the bonding property of the inorganic binder is facilitated, and the forming of the antibacterial artificial stone is further ensured.

The strength of the white Portland cement is 52.5-62.5 MPa, and the solid content of the polycarboxyl styrene-butadiene emulsion is not less than 50%.

In one embodiment of the technical scheme, white portland cement with the strength of 52.5-62.5 MPa is selected, so that the forming of the antibacterial artificial stone is ensured, and the hardness of the antibacterial artificial stone is improved. Meanwhile, the polycarboxy styrene-butadiene emulsion with solid content not less than 50 percent is adopted, so that the bonding performance of the inorganic binder can be effectively improved, and the forming of the antibacterial artificial stone is further ensured.

The technical solution of the present invention is further explained by the following embodiments.