CN111919857A - Preparation method of sterilization powder, sterilization powder and antibacterial inorganic artificial stone using sterilization powder - Google Patents
Preparation method of sterilization powder, sterilization powder and antibacterial inorganic artificial stone using sterilization powder Download PDFInfo
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Abstract
The invention discloses a preparation method of sterilization powder, the sterilization powder and an antibacterial inorganic artificial stone using the sterilization powder, and the preparation method of the sterilization powder comprises the following steps: A. mixing and heating a high molecular polymer, boric acid, potassium dihydrogen phosphate, copper sulfate, zinc acetate and water to form a sterilization adhesive; B. mixing the potassium feldspar powder and the titanium dioxide to form a mixed stirring material; C. kneading and pugging the sterilization adhesive liquid and the mixed and stirred materials to form plastic pug; D. sealing and curing the plastic pug, and putting the pug into a rotary kiln for rotary sintering; E. and adding the sintered plastic pug into a ball mill for ball milling. The preparation method of the sterilization powder provided by the technical scheme has the advantages of strong sterilization effect, simple operation and convenient preparation. Further provides the bactericidal powder prepared by the preparation method of the bactericidal powder, and the bactericidal effect is strong. Also provides an antibacterial inorganic artificial stone using the sterilizing powder, and the antibacterial rate of the artificial stone can reach 88 percent or more.
Description
Technical Field
The invention relates to the field of household appliances, in particular to a preparation method of sterilization powder, the sterilization powder and an antibacterial inorganic artificial stone using the sterilization powder.
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 inorganic 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 sterilization powder, which has the advantages of strong sterilization effect, simple operation and convenient preparation, and overcomes the defects in the prior art.
The invention also aims to provide the bactericidal powder prepared by the preparation method of the bactericidal powder, which has the advantages of strong bactericidal effect, high stability, good safety and environmental protection and low cost.
Another object of the present invention is to provide an antibacterial inorganic artificial stone using the above antibacterial powder, which has an antibacterial rate of 88% or more.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of sterilization powder comprises the following steps:
A. mixing and heating a high molecular polymer, boric acid, potassium dihydrogen phosphate, copper sulfate, zinc acetate and water to form a sterilization adhesive;
B. mixing the potassium feldspar powder and the titanium dioxide to form a mixed stirring material;
C. kneading and pugging the sterilization adhesive liquid and the mixed and stirred materials to form plastic pug;
D. sealing and curing the plastic pug, and putting the cured plastic pug into a rotary kiln for rotary sintering;
E. and adding the sintered plastic pug into a ball mill for ball milling to form the sterilization powder.
Preferably, in the step a, the bactericidal adhesive comprises the following raw material components in percentage by mass: 1-3% of high molecular 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.
Preferably, the high molecular polymer is any one of polyvinyl alcohol and methyl cellulose.
Preferably, in the step B, the mixing ratio of the potassium feldspar powder to the titanium dioxide is (21-95): 1, the fineness of the potassium feldspar powder is more than 200 meshes, and the fineness of the titanium dioxide is 2000 meshes.
Preferably, in the step of ball milling, the fineness of the bactericidal powder is 50-70 meshes.
A bactericidal powder is prepared by the preparation method of the bactericidal powder.
An antibacterial inorganic artificial stone, which comprises the antibacterial powder as raw materials;
the antibacterial inorganic artificial stone comprises the following raw materials in parts by weight: 10-15 parts of sterilization powder, 68-80 parts of artificial stone filler and 10-17 parts of 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 sterilization powder provided by the technical scheme has the advantages of strong sterilization effect, simple operation and convenient preparation, and overcomes the defects in the prior art. Further provides the bactericidal powder prepared by the preparation method of the bactericidal powder, which has the advantages of strong bactericidal effect, high stability, good safety and environmental protection and low cost. Also provides an antibacterial inorganic artificial stone using the sterilizing powder, and the antibacterial rate of the artificial stone can reach 88 percent or more.
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 powder of the invention.
Detailed Description
A preparation method of sterilization powder comprises the following steps:
A. mixing and heating a high molecular polymer, boric acid, potassium dihydrogen phosphate, copper sulfate, zinc acetate and water to form a sterilization adhesive;
B. mixing the potassium feldspar powder and the titanium dioxide to form a mixed stirring material;
C. kneading and pugging the sterilization adhesive liquid and the mixed and stirred materials to form plastic pug;
D. sealing and curing the plastic pug, and putting the cured plastic pug into a rotary kiln for rotary sintering;
E. and adding the sintered plastic pug into a ball mill for ball milling to form the sterilization powder.
The preparation method of the bactericidal powder sequentially comprises the steps of preparation of the bactericidal mucilage, mixing, pugging, sintering and ball milling.
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 inorganic artificial stone in the technical scheme 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 melting glass, 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, step E is followed by step F: the titanate surfactant is used for activating the sterilization powder, and then the sterilization powder is placed in an oven for drying treatment.
Preferably, in the step D, 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 a, the bactericidal adhesive comprises the following raw material components in percentage by mass: 1-3% of high molecular 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.
Specifically, the sterilization adhesive liquid comprises the following raw material components in percentage by mass: 1-3% of high molecular 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.
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 easy to reduce and tends to the plane structure of the boron-oxygen triangle, the chemical stability is also poor, and the sterilization effect of the sterilization powder is not ensured.
The zinc acetate and the copper sulfate have the same sterilization effect in the vitreous body, and the zinc acetate and the copper sulfate, the boric acid and the monopotassium phosphate are added into the sterilization adhesive liquid, so that the sterilization effect of the sterilization powder is further improved.
Further, the high molecular polymer is any one of polyvinyl alcohol and methyl cellulose.
Add the binder that high molecular polymer can regard as plasticity pug in the mucilage binding that disinfects, select for use polyvinyl alcohol or methylcellulose to add to the mucilage binding that disinfects as 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 bactericidal powder.
Further, in the step B, according to the mass ratio, the mixing ratio of the potassium feldspar powder to the titanium dioxide is (21-95): 1, the fineness of the potassium feldspar powder is more than 200 meshes, and the fineness of the titanium dioxide is 2000 meshes.
In the step B, according to the mass ratio, the mixing ratio of the potassium feldspar powder to the titanium dioxide is (21-95): 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 covering effect and the whitening effect can be achieved, and meanwhile, the titanium dioxide is also a photosensitive bactericidal antibacterial agent and is mixed with the potassium feldspar powder to be added into the plastic pug, so that the bactericidal effect of the bactericidal 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 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 powder can be effectively ensured while the requirements of the 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.
Further, in the step of ball milling, the fineness of the sterilization powder is 50-70 meshes.
When the fineness of the sterilization powder is too large, the surface area of the sterilization powder is correspondingly reduced, so that the glass leaching rate of the sterilization powder is reduced, and the improvement of the antibacterial rate of the inorganic artificial stone is not facilitated; when the fineness of the sterilization powder is too small, the glass leaching rate of the sterilization powder is easily increased, so that the effective duration time of sterilization is shortened, and the improvement of the whole antibacterial rate of the inorganic artificial stone is not facilitated.
Preferably, the fineness of the bactericidal powder is 60 meshes.
A bactericidal powder is prepared by the preparation method of the bactericidal powder.
An antibacterial inorganic artificial stone, which comprises the antibacterial powder as raw materials;
the antibacterial inorganic artificial stone comprises the following raw materials in parts by weight: 10-15 parts of sterilization powder, 68-80 parts of artificial stone filler and 10-17 parts of inorganic binder.
Furthermore, the technical scheme also provides an antibacterial inorganic artificial stone prepared by using the sterilization powder, which has the advantages of strong antibacterial effect, high stability, good safety and environmental protection and low cost.
In the technical scheme, the antibacterial inorganic artificial stone comprises the following raw material components: 10-15 parts of sterilization powder, 68-80 parts of artificial stone filler and 10-17 parts of inorganic binder, and is favorable for the antibacterial inorganic artificial stone to achieve the best antibacterial effect.
Further, the artificial stone filler is any one of a quartz filler, a marble filler, and a feldspar filler.
The sterilizing powder in the technical scheme is suitable for any one artificial stone filler of quartz stone filler, marble filler or feldspar filler, and has 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.
According to the technical scheme, the antibacterial inorganic artificial stone utilizes the inorganic adhesive to bond the antibacterial powder and the artificial stone filler, so that the prepared artificial stone is not easy to age and is low in cost.
Specifically, the white portland cement serves as an inorganic binder and a solid filler in the raw materials of the antibacterial inorganic artificial stone, so that the binding power of the inorganic binder can be effectively improved, the inorganic artificial stone can be formed conveniently, and the hardness of the antibacterial inorganic 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 inorganic 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 inorganic artificial stone is ensured, and the hardness of the antibacterial inorganic 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 molding of the antibacterial inorganic artificial stone is further ensured.
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example group 1-a method for preparing an antibacterial inorganic artificial stone, comprising the steps of:
A. mixing and heating high molecular polymer, boric acid, potassium dihydrogen phosphate, copper sulfate, zinc acetate and water according to the following table 1 to form sterilization adhesive liquid;
B. mixing the potassium feldspar powder and the titanium dioxide to form a mixed stirring material; the fineness of the potassium feldspar powder is 300 meshes, the fineness of the titanium dioxide is 2000 meshes, and the mixing ratio of the potassium feldspar powder to the titanium dioxide is 58: 1;
C. kneading and pugging the sterilization adhesive liquid and the mixed and stirred materials to form plastic pug;
D. sealing and curing the plastic pug, and putting the cured plastic pug into a rotary kiln for rotary sintering, wherein the sintering temperature of the plastic pug is 1100-1250 ℃;
E. adding the sintered plastic pug into a ball mill for ball milling to form sterilization powder, wherein the fineness of the sterilization powder is 60 meshes;
F. activating the sterilization powder by using a titanate surfactant, and then putting the sterilization powder into an oven for drying;
G. mix bactericidal powder and rostone filler, inorganic binder, form antibiotic inorganic rostone after carrying out suppression and thermosetting processing, wherein the mixing ratio of bactericidal powder, rostone filler and inorganic binder is 12: 74: 13, the inorganic binder consists of 20 parts of white portland cement, 10 parts of polycarboxyl butylbenzene emulsion, 2 parts of polycarboxylic acid water reducing agent and 1 part of tributyl phosphate, the artificial stone filler is feldspar filler, and the feldspar filler consists of 75 parts of feldspar sand, 40 parts of marble sand, 30 parts of quartz sand, 40 parts of feldspar powder, 30 parts of marble powder, 20 parts of quartz powder, 5 parts of titanium dioxide, 6 parts of iron oxide and 4 parts of carbon powder.
Table 1 raw material composition of bactericidal adhesive in example group 1
The sterilization powder and the antibacterial inorganic artificial stone are prepared by respectively adopting sterilization adhesive and mucilage of different raw material components in the table, the obtained sterilization powder is subjected to glass leaching rate test according to the following detection method, and the obtained antibacterial inorganic artificial stone is subjected to antibacterial rate test aiming at three different types of bacteria according to the antibacterial performance detection method JC/T897-2014 of the antibacterial ceramic product.
Testing the glass leaching rate:
(1) 100g of the sterilizing powder which is not subjected to activation treatment is weighed.
(2) Adding the bactericidal powder into a hydrochloric acid solution with the concentration of 2mol/L for soaking treatment, adding saturated ammonium chloride serving as a buffer solution into the hydrochloric acid solution, and putting the soaked bactericidal powder into a water bath constant-temperature pool with the temperature of 80 ℃ for water bath for 48 hours;
(3) then soaking the sterilization powder twice by using a large amount of distilled water, soaking for 24 hours for the first time and soaking for 24 hours for the second time, and then drying in an oven at 100 ℃.
(4) Weighing and calculating the leaching rate on a balance with the sensitivity of 0.001 g; wherein, the leaching rate is (m0-m)/m0 multiplied by 100 percent; wherein m0 is the sample mass before soaking and m is the sample mass after soaking.
The results are shown in table 2:
table 2 results of performance test of different antibacterial inorganic artificial stones in example group 1
The test results of example group 1 show that the glass leaching rate of the bactericidal powder prepared by the present example can reach 8% or more, and the antibacterial rate of the antibacterial inorganic artificial stone prepared by using the same can reach 88% or more.
Comparative example group 1-a method for preparing an antibacterial inorganic artificial stone, comprising the steps of:
A. mixing and heating high molecular polymer, boric acid, potassium dihydrogen phosphate, copper sulfate, zinc acetate and water according to the following table 3 to form sterilization adhesive liquid;
B. mixing the potassium feldspar powder and the titanium dioxide to form a mixed stirring material; the fineness of the potassium feldspar powder is 300 meshes, the fineness of the titanium dioxide is 2000 meshes, and the mixing ratio of the potassium feldspar powder to the titanium dioxide is 58: 1;
C. kneading and pugging the sterilization adhesive liquid and the mixed and stirred materials to form plastic pug;
D. sealing and curing the plastic pug, and putting the cured plastic pug into a rotary kiln for rotary sintering, wherein the sintering temperature of the plastic pug is 1100-1250 ℃;
E. adding the sintered plastic pug into a ball mill for ball milling to form sterilization powder, wherein the fineness of the sterilization powder is 60 meshes;
F. activating the sterilization powder by using a titanate surfactant, and then putting the sterilization powder into an oven for drying;
G. mix bactericidal powder and rostone filler, inorganic binder, form antibiotic inorganic rostone after carrying out suppression and thermosetting processing, wherein the mixing ratio of bactericidal powder, rostone filler and inorganic binder is 12: 74: 13, the inorganic binder consists of 20 parts of white portland cement, 10 parts of polycarboxyl butylbenzene emulsion, 2 parts of polycarboxylic acid water reducing agent and 1 part of tributyl phosphate, the artificial stone filler is feldspar filler, and the feldspar filler consists of 75 parts of feldspar sand, 40 parts of marble sand, 30 parts of quartz sand, 40 parts of feldspar powder, 30 parts of marble powder, 20 parts of quartz powder, 5 parts of titanium dioxide, 6 parts of iron oxide and 4 parts of carbon powder.
TABLE 3 raw Material Components for the germicidal cement of comparative example 1
Respectively adopting the sterilization adhesive and mucilage of different raw material components in the table to prepare sterilization powder and an antibacterial inorganic artificial stone, carrying out glass leaching rate test on the obtained sterilization powder, and carrying out antibacterial rate test on the obtained antibacterial inorganic artificial stone aiming at three different types of bacteria according to an antibacterial performance detection method JC/T897-2014 of the antibacterial ceramic product, wherein the results are shown in the following table 4:
table 4 results of performance test of different antibacterial inorganic artificial stones in comparative example group 1
As can be seen from the test results of examples 1-1, 1-3 and comparative examples 1-1 to 1-4, although the leaching rate of the sterilizing powder was good, the antibacterial rate of the antibacterial inorganic artificial stone was greatly reduced. It is known that boric acid and potassium dihydrogen phosphate have a complementary effect in the sterilization adhesive, and when the boric acid is too little, the phosphorus-oxygen tetrahedron tends to the plane structure of the phosphorus-oxygen trigonal body, so that the chemical stability is poor, and the sterilization effect is easily influenced; when the boric acid is excessive, the boron-oxygen tetrahedron is easy to reduce and tends to the plane structure of the boron-oxygen triangle, the chemical stability is also poor, and the sterilization effect of the sterilization powder is not ensured.
According to the test results of the examples 1-1 and 1-3 and the comparative examples 1-5 and 1-6, the zinc acetate and the copper sulfate have the same bactericidal effect in the vitreous body, and the addition of the zinc acetate and the copper sulfate, the boric acid and the potassium dihydrogen phosphate into the bactericidal adhesive paste is beneficial to further improving the bactericidal effect of the bactericidal powder. When the addition amount of the zinc acetate and the copper sulfate is too small, the sterilization effect is reduced to some extent, and when the addition amount of the zinc acetate and the copper sulfate is too large, although the sterilization effect of the antibacterial inorganic artificial stone is slightly increased, the color development of the artificial stone is poor due to too much copper sulfate in the sterilization adhesive liquid.
Example group 2-a method for preparing an antibacterial inorganic artificial stone, comprising the steps of:
A. mixing and heating 2% of polyvinyl alcohol, 2.5% of boric acid, 1.5% of potassium dihydrogen phosphate, 1.5% of copper sulfate, 2% of zinc acetate and the balance of water to form sterilization adhesive liquid;
B. mixing potassium feldspar powder and titanium dioxide according to the mixing proportion in the following table embodiment to form a mixed stirring material; wherein, the fineness of the potassium feldspar powder is 300 meshes, and the fineness of the titanium dioxide is 2000 meshes;
C. kneading and pugging the sterilization adhesive liquid and the mixed and stirred materials to form plastic pug;
D. sealing and curing the plastic pug, and putting the cured plastic pug into a rotary kiln for rotary sintering, wherein the sintering temperature of the plastic pug is 1100-1250 ℃;
E. adding the sintered plastic pug into a ball mill for ball milling to form sterilization powder, wherein the fineness of the sterilization powder is 60 meshes;
F. activating the sterilization powder by using a titanate surfactant, and then putting the sterilization powder into an oven for drying;
G. mix bactericidal powder and rostone filler, inorganic binder, form antibiotic inorganic rostone after carrying out suppression and thermosetting processing, wherein the mixing ratio of bactericidal powder, rostone filler and inorganic binder is 12: 74: 13, the inorganic binder consists of 20 parts of white portland cement, 10 parts of polycarboxyl butylbenzene emulsion, 2 parts of polycarboxylic acid water reducing agent and 1 part of tributyl phosphate, the artificial stone filler is feldspar filler, and the feldspar filler consists of 75 parts of feldspar sand, 40 parts of marble sand, 30 parts of quartz sand, 40 parts of feldspar powder, 30 parts of marble powder, 20 parts of quartz powder, 5 parts of titanium dioxide, 6 parts of iron oxide and 4 parts of carbon powder.
Example 2-1: the mixing ratio of the potassium feldspar powder to the titanium dioxide is 10: 1;
example 2-2: the mixing ratio of the potassium feldspar powder to the titanium dioxide is 21: 1;
examples 2 to 3: the mixing ratio of the potassium feldspar powder to the titanium dioxide is 95: 1;
examples 2 to 4: the mixing ratio of the potassium feldspar powder to the titanium dioxide is 120: 1;
the potash feldspar powder and the titanium dioxide pug with different mixing ratios in the above embodiments are respectively adopted to prepare the bactericidal powder and the antibacterial inorganic artificial stone, the obtained bactericidal powder is subjected to a glass leaching rate test, and the obtained antibacterial inorganic artificial stone is subjected to an antibacterial rate test for three different types of bacteria according to an antibacterial performance detection method JC/T897-2014 of the antibacterial ceramic product, and the results are shown in the following table 5:
table 5 results of performance test of different antibacterial inorganic artificial stones in example group 2
The test results of the example group 2 show that when the addition amount of the potassium feldspar powder in the mixed stirring 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, the formation of the boron-silicon-phosphorus glass ceramics is easily influenced, the leaching rate of the bactericidal powder is reduced, and the antibacterial rate is reduced; when the addition amount of the potassium feldspar powder in the mixed and stirred material is too much, the sintering of the plastic pug is not facilitated, the sintering temperature of the plastic pug is easily increased, and meanwhile, the antibacterial effect of the antibacterial inorganic artificial stone is also influenced.
Example group 3-a method for preparing an antibacterial inorganic artificial stone, comprising the steps of:
A. mixing and heating 2% of polyvinyl alcohol, 2.5% of boric acid, 1.5% of potassium dihydrogen phosphate, 1.5% of copper sulfate, 2% of zinc acetate and the balance of water to form sterilization adhesive liquid;
B. mixing the potassium feldspar powder and the titanium dioxide to form a mixed stirring material; wherein, the fineness of the potassium feldspar powder is 300 meshes, the fineness of the titanium dioxide is 2000 meshes, and the mixing ratio of the potassium feldspar powder to the titanium dioxide is 58: 1;
C. kneading and pugging the sterilization adhesive liquid and the mixed and stirred materials to form plastic pug;
D. sealing and curing the plastic pug, and putting the cured plastic pug into a rotary kiln for rotary sintering, wherein the sintering temperature of the plastic pug is 1100-1250 ℃;
E. adding the sintered plastic pug into a ball mill, and carrying out ball milling according to the fineness in the following examples to form sterilization powder;
F. activating the sterilization powder by using a titanate surfactant, and then putting the sterilization powder into an oven for drying;
G. mix bactericidal powder and rostone filler, inorganic binder, form antibiotic inorganic rostone after carrying out suppression and thermosetting processing, wherein the mixing ratio of bactericidal powder, rostone filler and inorganic binder is 12: 74: 13, the inorganic binder consists of 20 parts of white portland cement, 10 parts of polycarboxyl butylbenzene emulsion, 2 parts of polycarboxylic acid water reducing agent and 1 part of tributyl phosphate, the artificial stone filler is feldspar filler, and the feldspar filler consists of 75 parts of feldspar sand, 40 parts of marble sand, 30 parts of quartz sand, 40 parts of feldspar powder, 30 parts of marble powder, 20 parts of quartz powder, 5 parts of titanium dioxide, 6 parts of iron oxide and 4 parts of carbon powder.
Example 3-1: the fineness of the sterilization powder is 30 meshes;
example 3-2: the fineness of the sterilization powder is 50 meshes;
examples 3 to 3: the fineness of the sterilization powder is 70 meshes;
examples 3 to 4: the fineness of the sterilization powder is 90 meshes;
the antibacterial inorganic artificial stone is prepared by respectively adopting the bactericidal powders with different finenesses in the above embodiments, and the obtained bactericidal powder is subjected to a glass leaching rate test, and the obtained antibacterial inorganic artificial stone is subjected to an antibacterial rate test for three different types of bacteria according to an antibacterial performance detection method JC/T897-2014 of the antibacterial ceramic product, and the results are shown in the following table 6:
table 6 results of performance test of different antibacterial inorganic artificial stones in example group 3
The test result of the embodiment group 3 shows that when the fineness of the bactericidal powder is too large, the surface area of the bactericidal powder is correspondingly reduced, so that the glass leaching rate of the bactericidal powder is reduced, and the improvement of the antibacterial rate of the inorganic artificial stone is not facilitated; when the fineness of the sterilization powder is too small, the glass leaching rate of the sterilization powder is easily increased, so that the effective duration time of sterilization is shortened, and the improvement of the whole antibacterial rate of the inorganic artificial stone is not facilitated.
Example group 4-a method for preparing an antibacterial inorganic artificial stone, comprising the steps of:
A. mixing and heating 2% of polyvinyl alcohol, 2.5% of boric acid, 1.5% of potassium dihydrogen phosphate, 1.5% of copper sulfate, 2% of zinc acetate and the balance of water to form sterilization adhesive liquid;
B. mixing the potassium feldspar powder and the titanium dioxide to form a mixed stirring material; wherein, the fineness of the potassium feldspar powder is 300 meshes, the fineness of the titanium dioxide is 2000 meshes, and the mixing ratio of the potassium feldspar powder to the titanium dioxide is 58: 1;
C. kneading and pugging the sterilization adhesive liquid and the mixed and stirred materials to form plastic pug;
D. sealing and curing the plastic pug, and putting the cured plastic pug into a rotary kiln for rotary sintering, wherein the sintering temperature of the plastic pug is 1100-1250 ℃;
E. adding the sintered plastic pug into a ball mill for ball milling to form sterilization powder, wherein the fineness of the sterilization powder is 60 meshes;
F. activating the sterilization powder by using a titanate surfactant, and then putting the sterilization powder into an oven for drying;
and G, mixing the sterilization powder, the artificial stone filler and the inorganic binder, and performing pressing and thermosetting treatment to form the antibacterial inorganic artificial stone, wherein the sterilization powder, the artificial stone filler and the inorganic binder are mixed according to the mixing proportion of the following embodiments, the inorganic binder consists of 20 parts of white portland cement, 10 parts of polycarboxyl butylbenzene emulsion, 2 parts of polycarboxylic acid water reducing agent and 1 part of tributyl phosphate, the artificial stone filler is feldspar filler, and the feldspar filler consists of 75 parts of feldspar sand, 40 parts of marble sand, 30 parts of quartz sand, 40 parts of feldspar powder, 30 parts of marble powder, 20 parts of quartz powder, 5 parts of titanium dioxide, 6 parts of iron oxide and 4 parts of carbon powder.
Example 4-1:
the mixing ratio of the sterilization powder, the artificial stone filler and the inorganic binder is 5: 74: 13;
example 4-2:
the mixing ratio of the sterilization powder, the artificial stone filler and the inorganic binder is 10: 74: 13;
examples 4 to 3:
the mixing ratio of the sterilization powder, the artificial stone filler and the inorganic binder is 15: 74: 13;
examples 4 to 4:
the mixing ratio of the sterilization powder, the artificial stone filler and the inorganic binder is 25: 74: 13;
the antibacterial inorganic artificial stone is prepared by respectively adopting the bactericidal powder, the artificial stone filler and the inorganic binder with different mixing ratios in the above embodiments, and the obtained antibacterial inorganic artificial stone is subjected to an antibacterial rate test for three different types of bacteria according to an antibacterial performance detection method JC/T897-2014 of the antibacterial ceramic product, and the results are shown in the following table 7:
table 7 results of performance test of different antibacterial inorganic artificial stones in example group 4
| Antibacterial rate | Example 4-1 | Example 4 to 2 | Examples 4 to 3 | Examples 4 to 4 |
| Staphylococcus aureus | 89.2％ | 92.4％ | 90.4％ | 88.4％ |
| Candida albicans | 87.9％ | 90.6％ | 88.7％ | 86.2％ |
| Escherichia coli | 88.6％ | 91.8％ | 89.5％ | 87.3％ |
According to the test results of the embodiment group 4, the mixing ratio of the sterilization powder, the artificial stone filler and the inorganic binder is limited to (10-15): (68-80): (10-17), which is beneficial to the antibacterial inorganic artificial stone to achieve the best sterilization effect.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (10)
1. The preparation method of the sterilization powder is characterized by comprising the following steps:
A. mixing and heating a high molecular polymer, boric acid, potassium dihydrogen phosphate, copper sulfate, zinc acetate and water to form a sterilization adhesive;
B. mixing the potassium feldspar powder and the titanium dioxide to form a mixed stirring material;
C. kneading and pugging the sterilization adhesive liquid and the mixed and stirred materials to form plastic pug;
D. sealing and curing the plastic pug, and putting the cured plastic pug into a rotary kiln for rotary sintering;
E. and adding the sintered plastic pug into a ball mill for ball milling to form the sterilization powder.
2. The method for preparing a bactericidal powder according to claim 1, characterized in that: in the step A, the sterilization adhesive liquid comprises the following raw material components in percentage by mass: 1-3% of high molecular 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.
3. The method for preparing a bactericidal powder as claimed in claim 2, wherein the method comprises the following steps: the high molecular polymer is any one of polyvinyl alcohol or methyl cellulose.
4. The method for preparing a bactericidal powder according to claim 1, characterized in that: in the step B, according to the mass ratio, the mixing ratio of the potassium feldspar powder to the titanium dioxide is (21-95): 1, 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 a bactericidal powder according to claim 1, characterized in that: in the step of ball milling, the fineness of the sterilization powder is 50-70 meshes.
6. The bactericidal powder is characterized in that: the method for preparing the bactericidal powder of any one of claims 1 to 5.
7. An antibacterial inorganic artificial stone is characterized in that: the raw materials of the antibacterial powder comprise the antibacterial powder of claim 6;
the antibacterial inorganic artificial stone comprises the following raw materials in parts by weight: 10-15 parts of sterilization powder, 68-80 parts of artificial stone filler and 10-17 parts of inorganic binder.
8. An antibacterial inorganic artificial stone according to claim 7, characterized in that: the artificial stone filler is any one of quartz stone filler, marble filler or feldspar filler.
9. An inorganic artificial stone for door antibiosis according to claim 7, characterized in that: 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 inorganic artificial stone for door antibiosis according to claim 9, characterized in that: 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%.
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