阅读说明：本技术 一种抗菌人造石板材的制备方法及制备的抗菌人造石板材 (Preparation method of antibacterial artificial stone plate and prepared antibacterial artificial stone plate ) 是由 高忠麟 舒诚 于 2020-08-12 设计创作，主要内容包括：本发明公开了一种抗菌人造石板材的制备方法,包括以下步骤：混料步骤：将玻璃原料混合后,形成玻璃混合料；熔制步骤：将玻璃混合料熔制出可以溶出抗菌金属离子的硼硅酸盐玻璃；分相热处理步骤：将硼硅酸盐玻璃冷却后进行分相热处理；球磨步骤：将热处理后的硼硅酸盐玻璃进行球磨,形成抗菌玻璃粉；压制和热固化处理步骤：将抗菌玻璃粉与人造石板材填料、板材粘结剂混合,进行压制和热固化处理后形成抗菌人造石板材。本技术方案提出的一种抗菌人造石板材的制备方法,有利于提高人造石板材的抗菌率,且其稳定性高、安全环保性好、成本低。进而提出的一种使用上述抗菌人造石板材的制备方法所制备的抗菌人造石板材,其抗菌效果好。(The invention discloses a preparation method of an antibacterial artificial stone plate, which comprises the following steps: a material mixing step: mixing glass raw materials to form a glass mixture; melting: melting the glass mixture to prepare borosilicate glass capable of dissolving out antibacterial metal ions; phase separation heat treatment: cooling borosilicate glass and then carrying out split-phase heat treatment; ball milling: ball-milling the borosilicate glass after heat treatment to form antibacterial glass powder; pressing and heat curing treatment steps: and mixing the antibacterial glass powder with the artificial stone plate filler and the plate binder, and performing pressing and thermosetting treatment to form the antibacterial artificial stone plate. The preparation method of the antibacterial artificial stone plate provided by the technical scheme is beneficial to improving the antibacterial rate of the artificial stone plate, and has the advantages of high stability, good safety and environmental protection performance and low cost. The antibacterial artificial stone plate prepared by the preparation method of the antibacterial artificial stone plate has a good antibacterial effect.)

1. The preparation method of the antibacterial artificial stone slab is characterized by comprising the following steps of:

a material mixing step: mixing glass raw materials to form a glass mixture;

melting: melting the glass mixture to prepare borosilicate glass capable of dissolving out antibacterial metal ions; wherein the chemical components of the borosilicate glass comprise SiO in percentage by mass₂30～45％、B₂O₃20～35％、Al₂O₃1～3％、Na₂0 10～20％、TiO₂1-10% of ZnO and 1-10% of ZnO; the melting temperature of the borosilicate glass is 1350-1450 ℃;

phase separation heat treatment: cooling borosilicate glass and then carrying out split-phase heat treatment;

ball milling: adding the borosilicate glass subjected to heat treatment into a ball mill for ball milling to form antibacterial glass powder;

pressing and heat curing treatment steps: and mixing the antibacterial glass powder with the artificial stone plate filler and the plate binder, and performing pressing and thermosetting treatment to form the antibacterial artificial stone plate.

2. The method for preparing an antibacterial artificial stone slab as claimed in claim 1, wherein the method comprises the following steps: in the phase separation heat treatment step, the phase separation heat treatment temperature of the borosilicate glass is 550-650 ℃.

3. The method for preparing an antibacterial artificial stone plate as claimed in claim 2, wherein the method comprises the following steps: in the phase-splitting heat treatment step, the phase-splitting heat treatment time of the borosilicate glass is 1-2 h.

4. The method for preparing an antibacterial artificial stone slab as claimed in claim 1, wherein the method comprises the following steps: in the step of ball milling, the fineness of the antibacterial glass powder is more than or equal to 200 meshes.

5. The method for preparing antibacterial artificial stone slab as claimed in claim 1, wherein the steps of activating and drying are further included between the step of ball milling and the step of pressing and heat curing:

activating the antibacterial glass powder by using an activating solution, and then putting the activated glass powder into an oven for drying; the activating solution comprises the following raw material components in percentage by mass: 70% of methanol, 10% of water and 20% of surfactant.

6. The method for preparing an antibacterial artificial stone slab as claimed in claim 1, wherein the method comprises the following steps: according to the mass ratio, the mixing ratio of the antibacterial glass powder to the artificial stone plate filler to the plate binder is (3-4): 30: 270.

7. the method for preparing an antibacterial artificial stone plate as claimed in claim 6, wherein the method comprises the following steps: the plate binder comprises the following raw materials in parts by weight: 96-98.5 parts of unsaturated resin, 0.5-1.5 parts of curing agent, 0-0.5 part of accelerator and 1-2 parts of coupling agent.

8. The method for preparing an antibacterial artificial stone plate as claimed in claim 7, wherein the method comprises the following steps: the unsaturated resin is o-benzene unsaturated resin, the curing agent is cobalt octoate, the accelerator is methyl ethyl ketone peroxide, and the coupling agent is KH 570.

9. The method for preparing an antibacterial artificial stone plate as claimed in claim 7, wherein the method comprises the following steps: the artificial stone plate filler is any one of quartz plate filler, marble plate filler or feldspar plate filler.

10. An antibacterial artificial stone plate is characterized in that: the antibacterial artificial stone plate is prepared by using the preparation method of the antibacterial artificial stone plate as claimed in any one of claims 1 to 9.

Technical Field

The invention relates to the field of antibacterial plates, in particular to a preparation method of an antibacterial artificial stone plate and the prepared antibacterial artificial stone plate.

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 the functions of sterilization and antibiosis have become very popular abroad and have a basic requirement on stone materials.

The prior stone generally uses a bactericidal antibacterial agent containing silver ions, and the metal silver belongs to precious rare metals, so the price is high and the cost is high. Therefore, it is the most important obstacle to the popularization of stone materials with antibacterial and bactericidal functions. In addition, silver ions darken the color of the stone, which limits its application in some respects. At present, the bactericidal antibacterial agent comprises an organic bactericidal antibacterial agent and an inorganic bactericidal antibacterial agent, wherein the organic bactericidal antibacterial agent has a good bactericidal effect, but the effective time duration is short, and the organic bactericidal antibacterial agent is easy to lose efficacy. 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 artificial stone plate, which is beneficial to improving the antibacterial rate of the artificial stone plate, and has the advantages of high stability, good safety and environmental protection performance and low cost so as to overcome the defects in the prior art.

The invention also aims to provide the antibacterial artificial stone plate prepared by the preparation method of the antibacterial artificial stone plate, which has a good antibacterial effect.

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

a preparation method of an antibacterial artificial stone slab comprises the following steps:

a material mixing step: mixing glass raw materials to form a glass mixture;

melting: melting the glass mixture to prepare borosilicate glass capable of dissolving out antibacterial metal ions; the borosilicate glass comprises, by mass, 230-45% of SiO, 320-35% of B2O, 78-3% of Al2O31, 2010-20% of Na, 21-10% of TiO and 1-10% of ZnO, and the melting temperature of the borosilicate glass is 1350-1450 ℃;

phase separation heat treatment: cooling borosilicate glass and then carrying out split-phase heat treatment;

ball milling: adding the borosilicate glass subjected to heat treatment into a ball mill for ball milling to form antibacterial glass powder;

pressing and heat curing treatment steps: and mixing the antibacterial glass powder with the artificial stone plate filler and the plate binder, and performing pressing and thermosetting treatment to form the antibacterial artificial stone plate.

Preferably, in the step of phase separation heat treatment, the temperature of the phase separation heat treatment of the borosilicate glass is 550-650 ℃.

Preferably, in the step of phase separation heat treatment, the time of phase separation heat treatment of the borosilicate glass is 1-2 h.

Preferably, in the step of ball milling, the fineness of the antibacterial glass powder is more than or equal to 200 meshes.

Preferably, the ball milling step and the pressing and heat curing treatment step further comprise an activating and drying step:

activating the antibacterial glass powder by using an activating solution, and then putting the activated glass powder into an oven for drying; wherein the activating solution consists of the following raw material components: 70% of methanol, 10% of water and 20% of surfactant.

Preferably, the mixing ratio of the antibacterial glass powder to the artificial stone plate filler to the plate binder is (3-4): 30: 270.

preferably, the plate binder consists of the following raw materials in parts by weight: 96-98.5 parts of unsaturated resin, 0.5-1.5 parts of curing agent, 0-0.5 part of accelerator and 1-2 parts of coupling agent.

Preferably, the unsaturated resin is o-benzene type unsaturated resin, the curing agent is cobalt octoate, the accelerator is methyl ethyl ketone peroxide, and the coupling agent is KH 570.

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

An antibacterial artificial stone plate is prepared by the preparation method of the antibacterial artificial stone plate.

The invention has the beneficial effects that: the preparation method of the antibacterial artificial stone plate provided by the technical scheme is beneficial to improving the antibacterial rate of the artificial stone plate, and has the advantages of high stability, good safety and environmental protection performance and low cost so as to overcome the defects in the prior art. The antibacterial artificial stone plate prepared by the preparation method of the antibacterial artificial stone plate has a good antibacterial effect.

Detailed Description

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

A preparation method of an antibacterial artificial stone slab comprises the following steps:

a material mixing step: mixing glass raw materials to form a glass mixture;

melting: melting the glass mixture to prepare borosilicate glass capable of dissolving out antibacterial metal ions; wherein the chemical components of the borosilicate glass comprise SiO in percentage by mass₂30～45％、B₂O₃20～35％、Al₂O₃1～3％、Na₂0 10～20％、TiO₂1-10% of ZnO and 1-10% of borosilicate glass, wherein the melting temperature of the borosilicate glass is 1350-1450 ℃;

phase separation heat treatment: cooling borosilicate glass and then carrying out split-phase heat treatment;

ball milling: adding the borosilicate glass subjected to heat treatment into a ball mill for ball milling to form antibacterial glass powder;

pressing and heat curing treatment steps: and mixing the antibacterial glass powder with the artificial stone plate filler and the plate binder, and performing pressing and thermosetting treatment to form the antibacterial artificial stone plate.

The invention relates to a preparation method of an antibacterial artificial stone plate, which sequentially comprises the steps of mixing, melting, phase-splitting heat treatment, ball milling, pressing and thermosetting.

Specifically, according to the technical scheme, firstly, borosilicate glass is pre-melted, antibacterial ions Ti + + +, Zn + + are introduced into glass components in an oxide mode, TiO2 has a photosensitive sterilization function, and ZnO also has a photosensitive and dissolution dual sterilization function. Because the two antibacterial metal ions are not colored in the glass, the antibacterial metal ions can be optionally added into the artificial stone slab without causing any influence on the appearance of the artificial stone slab.

It should be noted that the borosilicate glass in the technical scheme can be prepared from conventional glass raw materials, and the borosilicate glass with the required chemical components in the technical scheme can be obtained by adjusting the types and the proportions of the glass raw materials. Preferably, in one embodiment of the present disclosure, the glass raw material of the borosilicate glass may include quartz sand, boric acid, aluminum hydroxide, sodium carbonate, titanium dioxide, and zinc oxide.

Then, carrying out phase-splitting heat treatment on the borosilicate glass, wherein after the phase-splitting heat treatment, the glass phase in the borosilicate glass is divided into a silicon-rich phase and a boron-rich phase, the boron-rich glass phase has subacidity and slight dissolubility in aqueous solution, and the acidity in a glass body is favorable for TiO₂ZnO is oxidized into high-valence Ti + + +, Zn + +, which is favorable for enabling Ti + + +, Zn + + to have strong bactericidal and antibacterial abilities, and boron-rich phase glass can release Ti + + +, Zn + + bactericidal and antibacterial ions after being slightly dissolved in aqueous solution, and the ions reach the surfaces of bacteria in contact with the boron-rich phase glass to kill the bacteria, thereby playing a role in sterilization and antibacterial. The antibacterial glass powder in the technical scheme has the advantages of simple preparation process, continuous and effective antibacterial action, sufficient raw material sources and convenience for common use in the artificial stone process with huge used materials.

Further, according to the mass percentage, the chemical components of the borosilicate glass in the technical scheme comprise SiO₂30～45％、B₂O₃20～35％、Al₂O₃1～3％、Na₂0 10～20％、TiO₂1-10% of ZnO and 1-10% of boron silicate glass, wherein the melting temperature of the boron silicate glass is 1350-145%0℃。

Wherein, Al₂O₃Is amphoteric oxide, and can absorb free oxygen to change from non-vitreous alundum to vitreous alundum into glass phase when the glass contains excessive free oxygen, so as to improve glass stability, hardness and strength₂O₃The boron silicon glass phase separation control agent also has the capacity of controlling the phase separation of the boron silicon glass, and can control the dissolution and precipitation of the boron glass, but the temperature of the molten glass is increased and the viscosity is increased due to the high content of the boron silicon glass. Na (Na)₂0 is not a glass forming body, provides free oxygen to the glass body to break glass tetrahedron or convert boron-oxygen triangle into boron-oxygen tetrahedron, improves the strength and chemical stability of the boron glass, and is beneficial to controlling the leaching rate of the glass. TiO2₂The glass is not a glass forming body and plays a role of a nucleating agent when being in phase-separated glass, and the technical scheme is introduced to play a double role of a photosensitive sterilizing antibacterial agent and a phase-separated nucleating agent. ZnO is also not a glass former, which reduces glass viscosity, and is introduced primarily for the purpose of photo-dissolution, sterilization and anti-bacterial action. In the technical scheme, the chemical components of the borosilicate glass are controlled, so that the antibacterial rate of the artificial stone plate is improved.

In the step of phase separation heat treatment, the temperature of the phase separation heat treatment of the borosilicate glass is 550-650 ℃.

The borosilicate glass can change the size of a microcrystalline region in a boron-rich phase and the release quantity and the sterilization effective duration of Ti + + +, Zn + + + -sterilization antibacterial ions by adjusting the temperature of the phase-splitting heat treatment.

When the temperature of the phase-splitting heat treatment is too low, the formed boron-rich area is smaller, the release quantity of the sterilization antibacterial ions is smaller, and the improvement of the antibacterial rate of the artificial stone plate is not facilitated; when the temperature of the phase separation heat treatment is too high, although the boron-rich glass phase is precipitated more and the phase forming area is larger, the borosilicate glass is excessively bonded by the too high temperature of the phase separation heat treatment, so that the effective duration of sterilization is shortened, and the whole antibacterial rate of the artificial stone plate is not improved.

In the step of phase separation heat treatment, the time of phase separation heat treatment of the borosilicate glass is 1-2 h.

The borosilicate glass can change the size of a microcrystalline region in a boron-rich phase and the release quantity and the sterilization effective duration of Ti + + +, Zn + + + -sterilization antibacterial ions by adjusting the time of phase-splitting heat treatment.

When the phase-splitting heat treatment time is too short, the boron-rich area formed by borosilicate glass is smaller, the release quantity of sterilization antibacterial ions is smaller, and the improvement of the antibacterial rate of the artificial stone plate is not facilitated; when the time of the phase separation heat treatment is too long, although the boron-rich glass phase is precipitated more and the phase forming area is larger, the sterilization effective duration time is influenced too short, and the improvement of the whole antibacterial rate of the artificial stone plate is also not facilitated.

Further, in the step of ball milling, the fineness of the antibacterial glass powder is more than or equal to 200 meshes.

Because the technical proposal is that SiO in the borosilicate glass₂The content is large, and in order to ensure that the antibacterial glass powder has satisfactory glass leaching rate, the technical scheme limits the fineness of the antibacterial glass powder to be more than or equal to 200 meshes. Therefore, when the fineness of the antibacterial glass powder is too large, the surface area of the antibacterial glass powder is correspondingly reduced, so that the glass leaching rate of the antibacterial glass powder is reduced, and the improvement of the antibacterial rate of the artificial stone plate is not facilitated; when the fineness of the antibacterial glass powder is too small, the glass leaching rate of the antibacterial glass powder is easily increased, so that the effective duration time of sterilization is shortened, and the improvement of the whole antibacterial rate of the artificial stone plate is not facilitated.

Further, the ball milling step and the pressing and heat curing treatment step also comprise an activating and drying step:

activating the antibacterial glass powder by using an activating solution, and then putting the activated glass powder into an oven for drying; wherein the activating solution consists of the following raw material components: 70% of methanol, 10% of water and 20% of surfactant.

In order to ensure that the antibacterial glass powder is uniformly dispersed in the raw material of the artificial stone plate, reduce the deposition phenomenon of the antibacterial glass powder and enhance the dispersion and bonding strength of the antibacterial glass powder in the raw material of the artificial stone plate, the technical scheme firstly activates the antibacterial glass powder by utilizing an activating solution.

Specifically, the activating solution adopted by the technical scheme comprises 70% of methanol, 10% of water and 20% of surfactant. Firstly, 70% of methanol and 10% of water solution are mixed to form a mixed solution, then acetic acid is used for adjusting the pH value of the mixed solution to 4-5 for dilution, then 20% of surfactant is added to form an activation solution, antibacterial glass powder is placed in a rotary cylinder and sprayed with the activation solution, and finally the antibacterial glass powder sprayed with the activation solution is placed in a 110 ℃ drying oven for drying treatment for 3 hours.

Preferably, the surfactant is KH570, i.e. gamma-methacryloxypropyltrimethoxysilane.

Further, the mixing ratio of the antibacterial glass powder, the artificial stone plate filler and the plate binder is (3-4): 30: 270.

in the technical scheme, the mixing ratio of the antibacterial glass powder, the artificial stone plate filler and the plate binder is limited to (3-4): 30: 270, which is beneficial to the antibacterial artificial stone plate to achieve the best antibacterial effect.

Further, the plate binder comprises the following raw materials in parts by weight: 96-98.5 parts of unsaturated resin, 0.5-1.5 parts of curing agent, 0-0.5 part of accelerator and 1-2 parts of coupling agent.

The board adhesive in the technical scheme consists of unsaturated resin, a curing agent, an accelerant and a coupling agent, wherein the unsaturated resin is the main adhesive component of the artificial stone board and is responsible for adhering the artificial stone board filler into stone with high strength. The curing agent, also called initiator, can generate free radicals to initiate the polymerization reaction between the styrene monomer in the unsaturated resin and the unsaturated resin to form the thermosetting resin after being decomposed. The accelerator can help the curing agent to accelerate the curing reaction and shorten the curing time. The coupling agent plays a role in combining the inorganic material with organic resin after the surface of the inorganic material is activated.

Further, the unsaturated resin is o-benzene type unsaturated resin, the curing agent is cobalt octoate, the accelerator is methyl ethyl ketone peroxide, and the coupling agent is KH 570.

The unsaturated resin generally comprises ortho-benzene type, meta-benzene type and para-benzene type, and the technical scheme ensures that the ortho-benzene type unsaturated resin is beneficial to bonding the artificial stone plate filler into the stone with high strength, and has low cost and good effect.

The technical scheme is that cobalt octoate is added into the artificial stone adhesive formula as the accelerator, so that the curing agent can generate enough free radicals to meet the curing reaction requirement.

Because the technical scheme is to produce the artificial stone plate, the main component of the artificial stone plate is silicon dioxide, and KH570 (gamma-methacryloxypropyltrimethoxysilane) is adopted as the coupling agent in the technical scheme in order to match the coupling agent with the plate raw material.

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

Preferably, the quartz stone plate 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 plate filler comprises the following raw material components:

furthermore, the quartz stone plate filler of the technical scheme is prepared by grading 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, so that the quartz stone plate is favorably ensured to have minimum gaps, the hardness and the strength of the quartz stone plate are enhanced, the using amount of unsaturated resin is reduced, and the production cost of the quartz stone plate is reduced. The quartz stone plate filler also comprises 0-5 parts of inorganic metal oxide colorant, so that the quartz stone plate filler can be used for coloring artificial stone plates, and the use experience of consumers is improved. More preferably, the inorganic metal oxide colorant is iron oxide.

Preferably, the marble plate 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 plate 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.

An antibacterial artificial stone plate is prepared by the preparation method of the antibacterial artificial stone plate.