阅读说明：本技术 一种抗菌有机人造石的制备方法及制备的抗菌有机人造石 (Preparation method of antibacterial organic artificial stone and prepared antibacterial organic artificial stone ) 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有机人造石的制备方法及制备的抗菌有机人造石,一种抗菌有机人造石的制备方法包括以下步骤：杀菌胶黏液制备步骤、混料步骤、练泥步骤、烧结步骤、球磨步骤和压制和热固化处理步骤。本技术方案提出的一种抗菌有机人造石的制备方法,有利于提高有机人造石的抗菌率,方法简单,操作性强,且制备过程能耗低,不会造成环境的污染,以克服现有技术中的不足之处。进而提出一种上述抗菌有机人造石的制备方法制备的抗菌有机人造石,其抗菌效果好。(The invention discloses a preparation method of an antibacterial organic artificial stone and the prepared antibacterial organic artificial stone, and the preparation method of the antibacterial organic artificial stone comprises the following steps: the preparation method comprises the steps of sterilization adhesive liquid preparation, material mixing, pugging, sintering, ball milling and pressing and thermosetting treatment. The preparation method of the antibacterial organic artificial stone provided by the technical scheme is beneficial to improving the antibacterial rate of the organic artificial stone, is simple, strong in operability, low in energy consumption in the preparation process, and free from environmental pollution, and overcomes the defects in the prior art. Further provides the antibacterial organic artificial stone prepared by the preparation method of the antibacterial organic artificial stone, and the antibacterial effect is good.)

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

the preparation method of the sterilization adhesive comprises the following steps: mixing and heating water-soluble high-molecular polymer, boric acid, potassium dihydrogen phosphate, copper sulfate, zinc acetate and water to form sterilization adhesive;

a material mixing step: mixing the potassium feldspar powder and the titanium dioxide to form a mixed stirring material;

pugging: kneading and pugging the sterilization adhesive liquid and the mixed and stirred materials to form plastic pug;

sintering: sealing and curing the plastic pug, and putting the cured plastic pug into a rotary kiln for rotary sintering;

ball milling: adding the sintered plastic pug into a ball mill for ball milling to form the sterilization microcrystalline glass powder;

pressing and heat curing treatment steps: and mixing the sterilizing microcrystalline glass powder with artificial stone filler and a bonding agent, and performing pressing and thermosetting treatment to form the antibacterial organic artificial stone.

2. The method for preparing an antibacterial organic artificial stone according to claim 1, wherein: in the preparation step of the bactericidal adhesive liquid, the bactericidal adhesive liquid comprises the following raw material components in percentage by mass: 1-3% of water-soluble high polymer, 2-3% of boric acid, 1-2% of monopotassium phosphate, 1-2% of copper sulfate, 1-3% of zinc acetate and the balance of water;

the water-soluble high molecular polymer is any one of polyvinyl alcohol or methyl cellulose.

3. The method for preparing an antibacterial organic artificial stone according to claim 1, wherein: in the material mixing step, according to the mass ratio, the mixing proportion of the potassium feldspar powder and the titanium dioxide is (21-95): 1.

4. the method for preparing an antibacterial organic artificial stone according to claim 3, wherein: the fineness of the potassium feldspar powder is more than 200 meshes, and the fineness of the titanium dioxide is 2000 meshes.

5. The method for preparing an antibacterial organic artificial stone according to claim 1, wherein: in the sintering step, the sintering temperature of the plastic pug is 1100-1250 ℃.

6. The method for preparing an antibacterial organic artificial stone according to claim 1, wherein: in the step of ball milling, the fineness of the bactericidal microcrystalline glass powder is 50-70 meshes.

7. The method for preparing an antibacterial organic artificial stone according to claim 1, wherein: according to the mass ratio, the mixing ratio of the sterilizing microcrystalline glass powder to the artificial stone filler to the binder is (10-15): (68-80): (10-17).

8. The method for preparing an antibacterial organic artificial stone according to claim 7, wherein: the adhesive comprises the following raw materials in parts by weight: 8-12 parts of unsaturated resin, 1-2 parts of curing agent, 0-1 part of accelerator and 1-2 parts of coupling agent.

9. The method of claim 8, wherein the method comprises the steps of: 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;

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

10. An antibacterial organic artificial stone is characterized in that: the artificial antibacterial stone is prepared by using the method for preparing the artificial antibacterial organic stone according to any one of claims 1 to 9.

Technical Field

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

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 antibacterial agent used for artificial stone is generally a purchased finished glass micro powder antibacterial agent or an organic antibacterial agent or a self-made antibacterial agent. The traditional glass-ceramic generation needs a glass melting furnace and a crucible or a glass continuous melting tank with complex equipment, precious metal platinum is used, the equipment investment is large in one time, the glass-ceramic melting temperature is about 1400-1500 ℃, the melting time is more than ten hours, the glass-ceramic formation generally needs secondary heat treatment to form glass-ceramic, and therefore the traditional glass-ceramic process is high in energy consumption, the introduced component decomposition and volatilization amount is large, and the environmental pollution is serious.

Disclosure of Invention

The invention aims to provide a preparation method of an antibacterial organic artificial stone, which is beneficial to improving the antibacterial rate of the organic artificial stone, has the advantages of simple method, strong operability, low energy consumption in the preparation process, no environmental pollution and capability of overcoming the defects in the prior art.

The invention also aims to provide the antibacterial organic artificial stone prepared by the preparation method of the antibacterial organic artificial stone, 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 organic artificial stone comprises the following steps:

the preparation method of the sterilization adhesive comprises the following steps: mixing and heating water-soluble high-molecular polymer, boric acid, potassium dihydrogen phosphate, copper sulfate, zinc acetate and water to form sterilization adhesive;

a material mixing step: mixing the potassium feldspar powder and the titanium dioxide to form a mixed stirring material;

pugging: kneading and pugging the sterilization adhesive liquid and the mixed and stirred materials to form plastic pug;

sintering: sealing and curing the plastic pug, and putting the cured plastic pug into a rotary kiln for rotary sintering;

ball milling: adding the sintered plastic pug into a ball mill for ball milling to form the sterilization microcrystalline glass powder;

pressing and heat curing treatment steps: and mixing the sterilizing microcrystalline glass powder with artificial stone filler and a bonding agent, and performing pressing and thermosetting treatment to form the antibacterial organic artificial stone.

Preferably, in the step of preparing the bactericidal adhesive liquid, the bactericidal adhesive liquid comprises the following raw material components in percentage by mass: 1-3% of water-soluble high polymer, 2-3% of boric acid, 1-2% of monopotassium phosphate, 1-2% of copper sulfate, 1-3% of zinc acetate and the balance of water;

the water-soluble high molecular polymer is any one of polyvinyl alcohol or methyl cellulose.

Preferably, in the material mixing step, the mixing ratio of the potassium feldspar powder to the titanium dioxide is (21-95): 1.

preferably, the fineness of the potassium feldspar powder is greater than 200 meshes, and the fineness of the titanium dioxide is 2000 meshes.

Preferably, in the sintering step, the sintering temperature of the plastic pug is 1100-1250 ℃.

Preferably, in the step of ball milling, the fineness of the bactericidal microcrystalline glass powder is 50-70 meshes.

Preferably, the mixing ratio of the sterilizing microcrystalline glass powder to the artificial stone filler to the binder is (10-15): (68-80): (10-17).

Preferably, the binder consists of the following raw material components in parts by mass: 8-12 parts of unsaturated resin, 1-2 parts of curing agent, 0-1 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;

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

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

The invention has the beneficial effects that: the preparation method of the antibacterial organic artificial stone provided by the technical scheme is beneficial to improving the antibacterial rate of the organic artificial stone, is simple, strong in operability, low in energy consumption in the preparation process, and free from environmental pollution, and overcomes the defects in the prior art. Further provides the antibacterial organic artificial stone prepared by the preparation method of the antibacterial organic artificial stone, and the antibacterial effect is good.

Drawings

The drawings are further illustrative of the invention and the content of the drawings does not constitute any limitation of the invention.

FIG. 1 is an X-ray diffraction pattern of the bactericidal glass-ceramic powder in the preparation method of the antibacterial organic artificial stone.

Detailed Description

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

the preparation method of the sterilization adhesive comprises the following steps: mixing and heating water-soluble high-molecular polymer, boric acid, potassium dihydrogen phosphate, copper sulfate, zinc acetate and water to form sterilization adhesive;

a material mixing step: mixing the potassium feldspar powder and the titanium dioxide to form a mixed stirring material;

pugging: kneading and pugging the sterilization adhesive liquid and the mixed and stirred materials to form plastic pug;

sintering: sealing and curing the plastic pug, and putting the cured plastic pug into a rotary kiln for rotary sintering;

ball milling: adding the sintered plastic pug into a ball mill for ball milling to form the sterilization microcrystalline glass powder;

pressing and heat curing treatment steps: and mixing the sterilizing microcrystalline glass powder with artificial stone filler and a bonding agent, and performing pressing and thermosetting treatment to form the antibacterial organic artificial stone.

The preparation method of the antibacterial organic artificial stone sequentially comprises the steps of preparation of a sterilization adhesive liquid, material mixing, pugging, sintering, ball milling, pressing and thermosetting treatment.

Specifically, according to the technical scheme, the metal oxide is introduced by a solution method to sinter the glass ceramics, and after the method is used, the sintering temperature of the glass ceramics is 200-300 ℃ lower than that of the glass ceramics which is prepared by directly introducing metal oxide powder, so that the energy consumption in the preparation process is greatly reduced.

In the technical scheme, potassium feldspar powder and titanium dioxide are selected as raw materials of the plastic pug, because the potassium feldspar powder and the titanium dioxide are water-soluble polymer binders, but general ceramic pugs are not cohesive, blanks have no strength during molding and cannot be basically molded, and after the potassium feldspar powder and the titanium dioxide are added, the ceramic pug has certain plasticity, can be made into the plastic pug meeting production requirements, and is convenient for subsequent sintering steps. After the plastic pug is sintered at high temperature in the rotary kiln, the sterilization metal oxide in the sterilization adhesive liquid reacts with the oxide inside the potassium feldspar to form the borosilicate phosphorus glass ceramic, and the sterilization metal ions exist in a zinc oxide or copper oxide glass body.

In the pugging step, the plastic pug formed by kneading the sterilization adhesive and the mixed stirring material needs to be bonded into a mass, and the plastic pug does not contain water after pugging is finished.

Compared with the traditional process for melting microcrystalline glass, the preparation method of the antibacterial organic artificial stone has the advantages that the equipment investment is less, the process is simple, the potassium feldspar has no volatile matter during sintering, the environmental protection requirement is met, the sintering temperature in the technical scheme is 200-300 ℃ lower than that of the traditional glass melting, the sintering time from feeding to discharging can be effectively reduced, and the microcrystalline glass is directly sintered (as shown in figure 1). Furthermore, the technical scheme of the invention does not need a secondary heat treatment process, so that the method has the advantages of energy conservation, environmental protection and short production period compared with the traditional microcrystalline glass melting process.

Preferably, the ball milling step and the pressing and heat curing treatment step further comprise an activating and drying step: and activating the sterilizing microcrystalline glass powder by using a titanate surfactant, and then putting the activated sterilizing microcrystalline glass powder into an oven for drying.

Further, in the step of preparing the bactericidal adhesive liquid, the bactericidal adhesive liquid comprises the following raw material components in percentage by mass: 1-3% of water-soluble high polymer, 2-3% of boric acid, 1-2% of monopotassium phosphate, 1-2% of copper sulfate, 1-3% of zinc acetate and the balance of water;

the water-soluble high molecular polymer is any one of polyvinyl alcohol or methyl cellulose.

Specifically, the sterilization adhesive liquid comprises the following raw material components in percentage by mass: 1-3% of water-soluble high polymer, 2-3% of boric acid, 1-2% of potassium dihydrogen phosphate, 1-2% of copper sulfate, 1-3% of zinc acetate and the balance of water.

Add water-soluble high molecular polymer and can regard as the binder of plasticity pug in the gluing liquid that disinfects, select for use polyvinyl alcohol or methylcellulose to add to the gluing liquid that disinfects as water-soluble high molecular polymer among this technical scheme, this is because polyvinyl alcohol or methylcellulose can volatilize basically after the sintering, is difficult to remain the borosilicate phosphorus glass ceramics that the oxide reaction of disinfecting metal oxide and potassium feldspar formed, is favorable to ensureing the bactericidal effect of the microcrystalline glass powder that disinfects.

Furthermore, in the technical scheme of the invention, the addition amount of boric acid is 2-3%, the addition amount of monopotassium phosphate is 1-2%, the boric acid reacts with potassium feldspar and is sintered into a glass body, phosphate and borate glass has acidic metal ions of Cu + +, Zn + +, and Ti + + +, and in the structure of the glass body, the acidic metal ions are in a high valence state, and the acidic metal ions in the high valence state can effectively oxidize bacteria to play a role in sterilization. Boric acid and potassium dihydrogen phosphate have a complementary effect in the sterilization adhesive, when the boric acid is too little, the phosphorus-oxygen tetrahedron tends to the plane structure of the phosphorus-oxygen trigonal body, the chemical stability is poor, and the sterilization effect is easily influenced; when the boric acid is excessive, the boron-oxygen tetrahedron is easily reduced and tends to the plane structure of the boron-oxygen triangle, the chemical stability is also deteriorated, and the sterilization effect of the sterilization microcrystalline glass powder is not ensured.

The zinc acetate and the copper sulfate also play a role in sterilizing in the vitreous body, and are added into the sterilization adhesive liquid together with the boric acid and the monopotassium phosphate, so that the sterilization effect of the sterilization microcrystalline glass powder is further improved.

Further, in the material mixing step, the mixing ratio of the potassium feldspar powder to the titanium dioxide is (21-95): 1.

in the material mixing step, the mixing proportion of the potassium feldspar powder and the titanium dioxide is (21-95) according to the mass ratio: 1; the sterilization metal oxide in the sterilization adhesive liquid reacts with the oxide in the potassium feldspar to form the borosilicate phosphorus glass ceramics, so that the sterilization and antibacterial effects are achieved; titanium dioxide is introduced into the mixed and stirred material, so that the functions of covering and whitening can be achieved, and meanwhile, the titanium dioxide is also a photosensitive bactericidal antibacterial agent, is mixed with the potassium feldspar powder and is added into the plastic pug, so that the bactericidal effect of the bactericidal microcrystalline glass powder can be further improved.

When the addition amount of the potassium feldspar powder in the mixed and stirred material is too small, the reaction between the bactericidal metal oxide in the bactericidal adhesive and the oxide in the potassium feldspar is not facilitated, and the formation of the borosilicate-phosphorus glass-ceramic is easily influenced; when the addition amount of the potassium feldspar powder in the mixed and stirred material is too large, the sintering of the plastic pug is not facilitated, and the sintering temperature of the plastic pug is easily increased.

Further, the fineness of the potassium feldspar powder is more than 200 meshes, and the fineness of the titanium dioxide is 2000 meshes.

The smaller the granularity of the potassium feldspar is, the more favorable the sintering is, the more effective the sintering temperature can be reduced, and the technical scheme adopts the potassium feldspar powder with the granularity of more than 200 meshes, so that the sterilization effect of the sterilization microcrystalline glass powder can be effectively ensured while the requirements of a sintering process are met.

The sintering temperature of the titanium dioxide is very high, so the technical scheme requires that the particles of the titanium dioxide are 2000 meshes, is beneficial to the reaction of the titanium dioxide, the potassium feldspar and other oxides, and can effectively reduce the sintering temperature of the plastic pug.

In the sintering step, the sintering temperature of the plastic pug is 1100-1250 ℃.

Because the microcrystalline glass is sintered by adopting the method of introducing the metal oxide by the solution method, after the method is used, the sintering temperature of the microcrystalline glass is 200-300 ℃ lower than that of the microcrystalline glass which is prepared by directly introducing the metal oxide powder, so that the plastic pug can be sintered within the range of 1100-1250 ℃, and the energy consumption generated in the preparation process is greatly reduced.

Further, in the step of ball milling, the fineness of the bactericidal microcrystalline glass powder is 50-70 meshes.

When the fineness of the sterilization microcrystalline glass powder is too large, the surface area of the sterilization microcrystalline glass powder is correspondingly reduced, so that the glass leaching rate of the sterilization microcrystalline glass powder is reduced, and the improvement of the antibacterial rate of the organic artificial stone is not facilitated; when the fineness of the sterilization glass-ceramic powder is too small, the glass leaching rate of the sterilization glass-ceramic powder is easily increased, so that the effective duration time of sterilization is shortened, and the improvement of the integral antibacterial rate of the organic artificial stone is not facilitated.

Preferably, the fineness of the bactericidal microcrystalline glass powder is 60 meshes.

Further, according to the mass ratio, the mixing ratio of the sterilizing microcrystalline glass powder to the artificial stone filler to the binder is (10-15): (68-80): (10-17).

In the technical scheme, the mixing proportion of the sterilization microcrystalline glass powder, the artificial stone filler and the binder is limited to (10-15): (68-80): (10-17), which is beneficial to the antibacterial organic artificial stone to achieve the best sterilization effect.

Further, the binder consists of the following raw material components in parts by mass: 8-12 parts of unsaturated resin, 1-2 parts of curing agent, 0-1 part of accelerator and 1-2 parts of coupling agent.

The 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 and is responsible for adhering the artificial stone 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 artificial stone filler is any one of quartz stone filler, marble filler or feldspar filler.

The unsaturated resin generally has an o-benzene type, an m-benzene type and a p-benzene type, and the technical scheme ensures that the o-benzene type unsaturated resin is beneficial to bonding the artificial stone filler into a stone with high strength, and has low cost and good effect.

The technical scheme is that cobalt octoate is added into a binder formula as an accelerator, so that the curing agent can generate enough free radicals to meet the requirements of curing reaction.

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

Further, the artificial stone filler in the technical scheme can be any one of quartz stone filler, marble filler or feldspar filler.

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:

specifically, the quartz stone 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 smallest gap of the quartz stone is favorably ensured, 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.

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

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.