KR20190101018A - Salt pan-floor tile with metal oxide layer capable of absorbing heavy metals and fabricating method thereof - Google Patents

Abstract

The present invention relates to a salt pan-floor tile used as a salt pan flooring material and a manufacturing method thereof and, more specifically, to a salt pan-floor tile forming a metal oxide layer on the surface removed from sea water by adsorbing harmful heavy metals included in sea water, and a manufacturing method thereof. The salt pan-floor tile having a metal oxide surface layer has a function of adsorbing heavy metals in sea water and a photocatalytic function of decomposing organic impurities in sea water, thereby being capable of producing environment-friendly salt without harmful heavy metals and organic impurities.

Description

Salt pan-floor tile with metal oxide layer capable of absorbing heavy metals and fabricating method

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a salt field tile used as a salt floor material and a method of manufacturing the same, and more particularly, a salt field tile having a metal oxide layer formed on a surface which can be removed from sea water by adsorbing harmful heavy metals contained in sea water. It relates to a manufacturing method.

Sea salt is a salt made by confining salt water and drying it with sunlight and wind. When saltwater is confined in salt water, a thin salt film is first formed on the surface of the saltwater, and then the salt crystals grow in size. As this crystal becomes heavier, it sinks down and the salt crystals stick to it, creating salt. These salts are coarse salts. If the thin film of salt is removed and dried separately before it sinks under water, the crystals become small. Salt is made.

   Jangpan, toppan, and ceramic tiles are mainly used as salt floors in the production of sun salt. Natural salt produced in Korea accounts for about 95% of enteropan salts made from jangpan, several% of toppan salts made from toppan, and several% of tile salts made from tiles. However, in the case of the top plate, the soil is frequently compacted with a roller or the like to keep the crystallized state in a solid state. The plate is made of synthetic resin [poly (vinyl chloride)], and the plate is easily made by using a straw when collecting salt. There are problems such as tearing or aging, elution of plasticizers and the like. Therefore, in recent years, top and floor plates have been replaced with ceramic tiles.

Salt water, which is the source of salt, contains most of the elements on the periodic table of the elements, 96.5% of which is pure water, and the rest consists of about 30 major elements. Among these components, heavy metals that are harmful to the human body, such as iron (Fe), copper (Cu), cobalt (Co), and manganese (Mn), and transition metals such as mercury (Hg), lead (Pb), and tin ( Metalloids such as Sn), selenium (Se), arsenic (As) and the like. The transition metals are toxic when absorbed or ingested in essential elements or in excess, depending on the type. In addition, the metalloids are not required in most cases depending on the species in the composition and metabolism of the organism, but in most cases are not necessary, and even at low concentrations, the metals may be fatal. In particular, metals such as mercury, copper, cadmium, and lead are more toxic than other metals. As such, seawater contains heavy metals that are harmful to the human body, and there is a problem in producing salts containing heavy metals because there is no process for removing these heavy metals in the salt manufacturing process. Although trace amounts of heavy metals, there is a problem that can accumulate in the human body when ingested by humans may cause various diseases.

Republic of Korea Patent No. 10-1590437 "Manufacturing method of breathable salt tile and its products" Korean Patent Registration No. 10-1785892 "Insulation Tile for Non-toxic Salt and Its Manufacturing Method" Republic of Korea Patent Registration No. 10-1635440 "Glass for Salt Salt Tile Containing Metal Silicon and Manufacturing Method of Salt Salt Tile Using the Same"

Silla Yeon et al., Korean Ceramics Research, Vol. 12 No.2, 127-141 (2016)

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and salt salt tiles having a metal oxide layer formed on the surface to adsorb harmful heavy metals contained in sea water in salt tiles to be removed from the sea water, and a method of manufacturing the same. To provide.

The object of the present invention is

In the salt tile having a metal oxide surface layer,

The metal oxide surface layer is formed of a surface coating mixture consisting of 30 to 98% by weight of a metal oxide powder, 1 to 40% by weight of a binder, and 10 to 60% by weight of a dispersion medium, and the metal oxide powder may contain or not contain a dopant. Salt field having a metal oxide surface layer, which is selected singly or in plural from TiO ₂ , ZnO, Fe ₂ O ₃ , Al ₂ O ₃ , MnO ₂ , CeO ₂ , MgO, SnO ₂ , V ₂ O ₃ , WO ₃ To provide a tile.

Still another object of the present invention is to provide a method for producing a salt tile having the metal oxide surface layer.

The metal oxide layer formed on the surface of the substrate tile by using the surface coating mixture of the present invention has a function of adsorbing heavy metals in seawater, and thus it is possible to produce salts containing no harmful heavy metals.

In addition, the metal oxide layer generates electrons excited by ultraviolet rays or visible rays included in sunlight, which can react with the organic impurities contained in seawater to decompose to produce salts containing no organic impurities.

As described above, the salt tile having the metal oxide surface layer of the present invention has a function of adsorbing heavy metals in seawater and a photocatalytic function of decomposing harmful organic impurities in seawater, thereby producing environmentally friendly salts containing no harmful heavy metals and organic impurities. There is a possible effect.

1 is a flowchart showing a step of forming a metal oxide surface layer after fabrication of a base tile in the manufacturing process of a salt tile having a metal oxide surface layer of the present invention.
2 is a flowchart illustrating a process of simultaneously heat treating a base tile and a metal oxide surface layer in a manufacturing process of a salt tile having a metal oxide surface layer of the present invention.
FIG. 3 is a graph showing the adsorption characteristic analysis (XPS) results of lead (Pb) in which the salt salt tile having the metal oxide surface layer according to Example 1 is a heavy metal.

The components and manufacturing steps of the salt generating tile having the metal oxide surface layer of the present invention will be described in detail with reference to FIG. 1 or FIG. 2.

<Manufacture of Base Tile for Salt Flooring>

The base tile for the salted flooring material can be easily manufactured by utilizing the prior art. The general manufacturing process of the base tile can be divided into a combination process, a grinding process, a granulation process, a molding process and a sintering process. The combination process is a process of mixing a well-purified raw material with a dispersion medium such as water, a binder, a lubricant, or a surfactant for a predetermined time. The raw material for manufacturing the base tile is ocher, pottery, feldspar, limestone, clay, cement, silica sand, loess loess, kaolin, clay, talc, ganban stone, glass, sand, mudflat, graphite, coal, etc. These raw materials, binders and additives may be mixed with a dispersion medium (water or organic solvent) to prepare a mixture in a slurry or paste state. The crushing process is a process of dispersing the raw materials into dispersion and fine particles (submicron ~ micron size) by using a ball mill (ball mill) equipment mixed. The granulation process is a process of manufacturing a spherical powder having a predetermined shape and size by instant drying the mixture of the slurry state after the grinding process with hot air. Spray drying is mainly used, and the granular powder formed has an average particle size of 60 to 80 µm. The molding process is a process of putting the spherical powder in a constant mold and applying heat and pressure to form a desired green body or green tile. The molding process includes dry pressing, hydrostatic pressure molding (CIP), injection molding (Slip Casting), Extrusion, Injection Molding, Hot Isostatic Press (Gas Pressing Sintering) and the like are possible. A sintering process is a process of heat-processing the said molded object in the high temperature (700-1500 degreeC) baking furnace. By heating or heating the molded body to a high temperature, densification to remove pores existing between the particles, melting of the particles, and grain growth occur. On the other hand, between the molding process and the sintering process may further include a milking process for applying a glaze on the surface of the molded body.

<Formation of metal oxide layer on surface of base tile>

In order to form a metal oxide layer on the surface layer of the substrate tile, first, a surface coating mixture is prepared, and the surface is coated (coated process) and then heat treated (heat treatment process). The manufacture of tiles is possible.

The surface coating mixture is based on 30 to 98% by weight of the metal oxide powder, 1 to 40% by weight of the binder (binder) and 10 to 60% by weight of the dispersion medium. The metal oxide powder and the binder are added to the dispersion medium, followed by mixing and milling to finely disperse the metal oxide powder to prepare a surface coating mixture. Examples of the metal oxides include TiO ₂ , ZnO, Fe ₂ O ₃ , Al ₂ O ₃ , MnO ₂ , CeO ₂ , MgO, SnO ₂ , V ₂ O ₃ , WO ₃ , and the like. It can be produced in a porous manner, (2) it can effectively adsorb heavy metals, and (3) has a photocatalyst function that can absorb ultraviolet rays and decompose organic matter. Meanwhile, the metal oxide may be used in a doped form, and the dopant required for doping may be used alone or in Zr, N, Pt, B, C, F, Al, Ga, In Si, Ge, or the like. Plural can be selected. Taking nitrogen-doped TiO ₂ (N-doped TiO ₂ ) as an example, a precursor of nitrogen (N) as a dopant is added to the manufacturing process by adding triethyl amine or hexadecyl trimethyl ammonium to TiO ₂ to proceed with the synthesis reaction. TiO ₂ (N-doped TiO ₂ ) may be prepared. Since the doped metal oxide is capable of absorbing visible light, the photocatalyst function is expressed by the visible light. The metal oxide powder in the surface coating mixture is suitably 30 to 98% by weight. If the content of the metal oxide powder is less than 30%, there is a problem that the adsorption of heavy metals and decomposition of impure organic matter are reduced due to the small amount of metal oxide due to excessive voids in the surface layer. There is a problem that the coating film is easily deformed by external impact, contact or the like.

The binder may be an organic binder or an inorganic binder. The organic binder may be acrylic resin, vinyl resin, olefin resin, fluorine resin, silicone resin, phenol resin, melamine resin, urea resin, polyamide resin, polyester resin, alkyd resin, polycarbonate resin, poly Polymeric materials, such as a urethane resin, an epoxy resin, a cellulose polymer, etc. are mentioned. Examples of the inorganic binder include cement, gypsum, mud, clay, silica, sodium silicate, aluminum silicate, calcium silicate, and frit glass. 1 ~ 40% by weight of the binder of the surface coating mixture is appropriate, if less than 1% by weight is a problem that the coating film coated on the surface of the substrate tile is easily deformed by external impact, contact, etc., the surface layer is more than 40% Too much pore of the metal oxide content is low, there is a problem that the adsorption of heavy metals and decomposition of impurities organic matter is reduced.

The dispersion medium serves as a medium for dispersing the metal oxide. When the binder is an organic polymer compound, the dispersion medium also includes a function of a solvent for dissolving the polymer. These dispersion media include water, ethanol, isopropyl alcohol, methanol, acetone, hexanol, propanol, butylalcohol and tertiary. Tertiary butylalcohol, acetonitrile, tetrahydrofuran, methylethylketone, formamide, N-methylformamide, N, N- Dimethylformamide (N, N-dimethylformamide), acetamide (acetamide), N-methylacetamide, N, N-dimethylacetamide (N, N-dimethylacetamide), N-methylpropionamide (N -methylpropionamide, pyrrolidone, 2-pyrrolidone, N-methyl pyrrolidone, methyl sulfoxide, dimethyl sulfoxide, dimethyl sulfoxide, sulfolane, di Phenyl sulfone, trihydrofuran, methyl ethyl ketone, ethyl ether, Ether, dichloromethane, can be used methane tetrachloride, chloroform, benzene, toluene, xylene and the like, either alone or in plurality, but the invention is not limited to these.

The dispersion medium in the surface coating mixture is suitably 10 to 60% by weight. If the content of the dispersion medium is less than 10% by weight, there is a problem in that the surface coating mixture is poorly mixed to form a non-uniform metal oxide surface layer. If the content is more than 60% by weight, the viscosity of the surface coating mixture is difficult to handle. There is a problem in that the thickness of the and the porosity is too small to reduce the content of metal oxides to reduce the effect of adsorption of heavy metals and decomposition of impurities organic matter.

The surface coating mixture of the present invention is a basic composition of the metal oxide powder, the binder and the dispersion medium, but may further include an additive. The additive may further include a blowing agent, a dispersant, an antifoaming agent, and the like. As the blowing agent, p, p'-oxybis (benzenesulfonyl hydrazide) [p, p'-oxybis (benzenesulfonyl hydrazide; OBSH), benzenesulfonyl hydrazide, azobisformamide, Azodicarbonamide (ADCA), dinitroso pentamethylenetetramine (DPT), p-toluenesulfonylhydrazide (TSH), p-toluenesulfonyl semicarbazide organic blowing agents such as (p-toluene sulfonylsemicarbazide; PTSS), CFC-11 (CFCl ₃ ), CFC-12 (CF ₂ Cl ₂ ), FC-113 (ClF ₂ C-CFCl ₂ ), HCFC-22 (HF ₂ CCl Chlorofluorocarbon blowing agents such as), sodium bicarbonate (NaHCO ₃ ), ammonium bicarbonate (NH ₄ HCO ₃ ), ammonium carbonate ((NH ₄ ) ₂ CO ₃ ), ammonium nitrite (NH ₄ NO ₂ ), sodium hydrogen borohydride And inorganic blowing agents such as (NaBH ₄ ) and Ca (N ₃ ) ₂ (azide compounds). The surface coating mixture including these blowing agents is coated on the surface of the substrate tile, and thermal decomposition of the blowing agent occurs in the heat treatment step to generate gases such as CO ₂ , H ₂ O, N ₂ , CO, CO ₂ , NH ₃ , NOx, HCHO, and the like. It is possible to form a metal oxide layer having a porous structure. As such, the metal oxide layer having a porous structure has an advantage of increasing the adsorption rate and the amount of adsorption of heavy metals contained in seawater. In addition, by providing a passage through which sunlight can penetrate to the lower portion of the metal oxide surface layer, the photocatalytic effect is improved, and there is an advantage of minimizing harmful components by decomposing impurity organic compounds contained in seawater. Since the surface layer of the porous metal oxide can be formed by the use of a blowing agent, there is an advantage of improving the efficiency of removing heavy metals and the efficiency of photocatalysis which decomposes impurities, and thus, does not contain heavy metals and impurity organic compounds. It is possible to produce eco-friendly salt that does not contain.

The dispersant may be included to evenly disperse the metal oxide powder in the dispersion medium, nonionic surfactants such as fatty acid polyoxyethylene alkyl ether, fatty acid sorbitan ester, fatty acid diethanolamine, alkyl monoglyceryl ether, Fatty acid sodium, monoalkyl sulfate, alkyl polyoxyethylene sulfate, alkylbenzene sulfonate, monoalkyl phosphate, alkyl-2-sulfoxyethoxyacetamide sodium salt, sodium laureth sulfate, decyl-2- sulfoxyethoxyacetamide Anionic surfactants such as sodium salts, myristyl-2-sulfoxyethoxyacetamide sodium salts, palmityl-2-sulfoxyethoxyacetamide sodium salts, stearyl-2-sulfoxyethoxyacetamide sodium salts, and the like, Cationic surfactants such as dialkyldimethylammonium salts, alkylbenzylmethylammonium salts, alkylsulfobetaines, alkylcarboxybetaines and the like Is not the present invention there can be an amphoteric surfactant for example is not limited thereto.

The antifoaming agent may include an antifoaming agent to remove bubbles contained in the surface coating mixture. The antifoaming agent may be a mineral oil antifoaming agent, a silicone antifoaming agent, a polymer antifoaming agent, or the like, but is not limited thereto.

The method of coating the surface coating mixture of the present invention on the substrate tile may include doctor blade coating, knife coating, screen printing, spray coating, slit die coating, Electrostatic coating, bar coating, flexography, gravure printing, etc. are possible.

The metal oxide surface layer is formed by a heat treatment process in which heat is applied to the surface coating mixture coated on the surface of the base tile to fuse the metal oxide particles, wherein the temperature of the heat treatment process is appropriately 300 to 1300 ° C. In this heat treatment process, the organic materials (organic binder, organic foaming agent, organic dispersant, organic antifoaming agent, etc.) included in the surface coating mixture are decomposed into gas and thus do not remain in the final metal oxide surface layer. The thickness of the metal oxide surface layer after the heat treatment process depends on the thickness of the base tile, but 1μm ~ 5cm is appropriate, the thickness can be adjusted according to the coating method and the number of coating.

On the other hand, using the surface coating mixture of the present invention as a method for producing a salt oxide tile having a metal oxide surface layer, as shown in Figure 1 first to produce a base tile [combining process, grinding process, granulation process, molding process, sintering ] And then coating the surface coating mixture on its surface is possible by a coating process and a heat treatment process. In addition, as shown in FIG. 2, the coating process for coating the surface coating mixture between the forming process and the sintering process in the substrate tile manufacturing process is performed. It is possible. As described above, the preparation of the salt-based tile having the metal oxide surface layer according to the present invention is first performed in the order of the base tile manufacturing process (combination process, grinding process, assembly process, molding process, sintering process), surface coating mixture coating process and heat treatment process. And second, a combination process, a grinding process, an assembly process, a molding process, a surface coating mixture coating process and a sintering process are possible.

Example

Hereinafter, the salt metal having the metal oxide surface layer of the present invention and a method for preparing the same are embodied by way of examples, but the present invention is only presented to aid the understanding of the present invention, and the present invention is not limited to the following examples.

Example  One

65 g of TiO ₂ powder as a metal oxide was added to an aqueous solution of cellulose (5 g of carboxymethyl cellulose sodium + 20 g of water), followed by mixing using a milling apparatus, thereby preparing a surface coating mixture. The surface coating mixture was coated on the surface of a salt salt tile separately prepared by doctor blade coating, followed by heat treatment at 500 ° C. for 60 minutes to decompose and remove the organic binder carboxymethyl cellulose sodium, thereby fusion of the metal oxide. The salt tile having the metal oxide surface layer thus prepared was deposited in a 50mM Pb (NO ₃ ) ₂ aqueous solution for 40 minutes to adsorb heavy metal lead ions onto the metal oxide surface. The salt tiles were removed from the Pb (NO ₃ ) ₂ aqueous solution and the residual aqueous solution was analyzed by atomic absorption spectroscopy. As a result, it was confirmed that 398 mg of lead ions were adsorbed per 1 g of the metal oxide (TiO ₂ ).

In addition, XPS analysis was carried out after preparing the specimens with different deposition times when salt salts having a metal oxide surface layer were deposited in Pb (NO ₃ ) ₂ aqueous solution, and the results are shown in FIG. 3. Lead (Pb) was not detected in the salt layer surface layer that was not immersed in Pb (NO ₃ ) ₂ solution, but after immersion in the aqueous solution, the peak due to lead appeared at 140.02 eV. Increased. As a result, it was found that TiO ₂ can effectively remove intermediate lead.

Example  2

Salt salt tile having a metal oxide surface layer was prepared under the same conditions as in Example 1 except that 4 g of ammonium carbonate [(NH ₄ ) ₂ CO ₃ ] as a blowing agent was added to the surface coating mixture of Example 1. Salt metal having the prepared metal oxide surface layer was deposited in 50mM Pb (NO ₃ ) ₂ aqueous solution to adsorb heavy metal lead ions onto the metal oxide surface. The salt tiles were removed from the Pb (NO ₃ ) ₂ aqueous solution and the residual aqueous solution was analyzed by atomic absorption spectroscopy. As a result, it was confirmed that 632 mg of lead ions were adsorbed per 1 g of the metal oxide (TiO ₂ ). From this, a porous metal oxide layer was formed by the presence of a blowing agent, and it was confirmed that the adsorption efficiency of lead, which is a heavy metal, was improved during the same time due to an increase in surface area.

Example  3

ZnO powder 32g, MgO powder 25g as metal oxide, NaHCO _{3 as} blowing agent 3g, 0.5g of naphthalene sulfonatesodium sa1t as a dispersant was added to a poly (vinyl alcohol) aqueous solution [poly (vinyl alcohol) 1g + water 17g] and then mixed using a milling apparatus to prepare a surface coating mixture. The surface coating mixture was coated on the surface of the salt salt tile separately prepared by spray coating, followed by heat treatment at 750 ° C. for 30 minutes to sinter the organic binder poly (vinyl alcohol) and the dispersant, and simultaneously foam the NaHCO ₃ to form the upper surface of the base tile. A porous metal oxide surface layer was formed on the substrate. The salt tile having the metal oxide surface layer thus prepared was immersed in an aqueous solution of Cd (NO ₃ ) _{2 at a} concentration of 30 mM for 1 hour to adsorb heavy metal cadmium ions onto the surface of the metal oxide. The salt tiles were removed from the aqueous solution of Cd (NO ₃ ) ₂ , and the residual aqueous solution was analyzed by atomic absorption spectroscopy. As a result, 496 mg of cadmium ions were adsorbed per 1 g of metal oxide (ZnO + MgO).

In addition, XPS analysis was performed after preparing specimens with different deposition times when depositing salted metals having a metal oxide surface layer in Cd (NO ₃ ) ₂ aqueous solution. As a result, salted tiles not deposited in Cd (NO ₃ ) ₂ aqueous solution. Cadmium (Cd) was not detected in the surface layer, but after deposition in aqueous solution, the peak by cadmium appeared at 405.1 eV, and the area of the peak increased with increasing deposition time. As a result, it was found that the metal oxide surface layer can effectively remove intermediate cadmium.

Example  4

23 g of Fe ₂ O ₃ powder, 12 g of MnO ₂ powder, 1.5 g of azobisformamide, a foaming agent, 0.5 g of KS-66 from Shin-Etsu Co., Ltd. cellosolve) and then mixed using a milling equipment to prepare a surface coating mixture. The surface coating mixture was coated on the surface of the salt salt tile separately prepared by knife coating and heat-treated at 1000 ° C. for 30 minutes to sinter the organic binder poly (methyl methacrylate) and foam the azobisformamide at the same time as the upper surface of the base tile A porous metal oxide surface layer was formed on the substrate. The salted tile having the metal oxide surface layer prepared as described above was immersed in a 60 mM Co (NO ₃ ) ₂ aqueous solution for 1 hour to adsorb heavy metal cobalt ions onto the surface of the metal oxide. The salt tiles were removed from the CoNO ₃ ) ₂ solution and the residual aqueous solution was analyzed by atomic absorption spectroscopy. As a result, it was confirmed that 511 mg of cobalt ions were adsorbed per 1 g of the metal oxide (Fe ₂ O ₃ + MnO ₂ ). In addition, XPS analysis was performed after preparing specimens with different deposition times when depositing salt salts with metal oxide surface layers in Co (NO ₃ ) ₂ aqueous solution, and as a result, salt salt tiles not deposited in Co (NO ₃ ) ₂ aqueous solution. Cobalt (Co) was not detected in the surface layer, but after deposition in aqueous solution, a peak due to cobalt appeared at 779.7 eV, and the area of the peak increased as the deposition time increased. As a result, it was found that the metal oxide surface layer can effectively remove intermediate cobalt.

Claims (13)

In the salt tile having a metal oxide surface layer,
The metal oxide surface layer is formed of a surface coating mixture consisting of 30 to 98% by weight of a metal oxide powder, 1 to 40% by weight of a binder, and 10 to 60% by weight of a dispersion medium, and the metal oxide powder may contain or not contain a dopant. Salt field having a metal oxide surface layer, which is selected singly or in plural from TiO ₂ , ZnO, Fe ₂ O ₃ , Al ₂ O ₃ , MnO ₂ , CeO ₂ , MgO, SnO ₂ , V ₂ O ₃ , WO ₃ tile.
The method according to claim 1,
The surface coating mixture may further include a blowing agent, and as the blowing agent, p, p'-oxybis (benzenesulfonyl hydrazide) [p, p'-oxybis (benzenesulfonyl hydrazide)], benzenesulfonyl hydrazide ( benzenesulfonyl hydrazide, azobisformamide, azodicarbon amide, dinitroso pentamethylenetetra mine, p-toluenesulfonyl hydrazide, p-toluenesulfonyl hydrazide Organic blowing agents such as p-toluene sulfonyl semicarbazide, chloroflruorocarbon blowing agents such as CFCl ₃ , CF ₂ Cl ₂ , ClF ₂ C-CFCl ₂ , HF ₂ CCl, sodium bicarbonate, NaHCO ₃ ), ammonium bicarbonate (NH ₄ HCO ₃ ), ammonium carbonate ((NH ₄ ) ₂ CO ₃ ), ammonium nitrite (NH ₄ NO ₂ ), sodium hydrogen borohydride (NaBH ₄ ), Ca (N ₃ ) ₂ (azide Single or plural from inorganic blowing agents composed of Salt tile having a metal oxide surface layer characterized in that the selection. The method according to claim 1,
The surface coating mixture may further include a dispersant, and the dispersant may be a nonionic surfactant such as fatty acid polyoxyethylene alkyl ether, fatty acid sorbitan ester, fatty acid diethanolamine, alkyl monoglyceryl ether, fatty acid sodium, mono Alkyl sulfate, alkyl polyoxyethylene sulfate, alkylbenzene sulfonate, monoalkyl phosphate, alkyl-2- sulfoxy ethoxy acetamide sodium salt, sodium laureth sulfate, decyl-2- sulfoxy oxy acetamide sodium salt, previously Anionic surfactants such as stil-2-sulfoxyethoxyacetamide sodium salt, palmityl-2-sulfoxyethoxyacetamide sodium salt, stearyl-2-sulfoxyethoxyacetamide sodium salt, dialkyldimethylammonium salt From cationic surfactants such as alkylbenzylmethylammonium salts, amphoteric surfactants such as alkylsulfobetaines, alkylcarboxybetaines Or torsion tile having a metal oxide surface layer characterized in that the selection of a plurality.
The method according to claim 1,
The surface coating mixture may further comprise an antifoaming agent, wherein the antifoaming agent is a salt oil tile having a metal oxide surface layer, characterized in that it is selected singly or plurally from mineral oil antifoaming agent, silicone antifoaming agent, polymer antifoaming agent.
The method according to claim 1,
The binder is an acrylic resin, vinyl resin, olefin resin, fluorine resin, silicone resin, phenol resin, melamine resin, urea resin, polyamide resin, polyester resin, alkyd resin, polycarbonate resin, polyurethane resin , Metal oxide surface layer selected from organic binders such as epoxy resins, inorganic binders such as cement, gypsum, mud, clay, silica, sodium silicate, aluminum silicate, calcium silicate, frit glass, etc. Salt salt tile having.
The method according to claim 1,
The dispersion medium is water (ethanol), isopropyl alcohol (isopropyl alcohol), methanol (methanol), acetone (acetone), hexanol (hexanol), propanol (butyl alcohol), butyl alcohol (butylalcohol), ter Tertiary butylalcohol, acetonitrile, tetrahydrofuran, methylethylketone, formamide, N-methylformamide, N, N- Dimethylformamide (N, N-dimethylformamide), acetamide (acetamide), N-methylacetamide, N, N-dimethylacetamide (N, N-dimethylacetamide), N-methylpropionamide (N -methylpropionamide, pyrrolidone, 2-pyrrolidone, N-methyl pyrrolidone, methyl sulfoxide, dimethyl sulfoxide, dimethyl sulfoxide, sulfolane, di Phenyl sulfone, trihydrofuran, methyl ethyl ketone, ethyl ether, di Butyl ether, salt tiles with dichloromethane, methane tetrachloride, chloroform, benzene, toluene, xylene and the like metal oxide, characterized in that the surface layer is selected from a single or plural. The method according to claim 1,
And the dopant is selected from the group consisting of Zr, N, Pt, B, C, F, Al, Ga, In.
Preparing a base tile;
A coating step of forming a film by coating a surface coating mixture consisting of a metal oxide powder, a binder, and a dispersion medium on the substrate tile;
It consists of a heat treatment step of fusion of the metal oxide by applying heat to the coating film,
The metal oxide powder is selected from dopant-containing or non-doping TiO ₂ , ZnO, Fe ₂ O ₃ , Al ₂ O ₃ , MnO ₂ , CeO ₂ , MgO, SnO ₂ , V ₂ O ₃ , WO ₃ A method of producing a salt tile having a metal oxide surface layer, characterized in that.
The method according to claim 8,
The base tile is
A mixing step of mixing the raw material for the base tile;
Milling the mixed raw materials to separate them into fine particles;
A granulation step of drying the ground mixture with hot air to produce granules having a predetermined shape and size;
And putting the granular powder into a predetermined mold and then applying heat and pressure to form a desired molded body.
The method according to claim 8,
The surface coating mixture may further include a blowing agent, and as the blowing agent, p, p'-oxybis (benzenesulfonyl hydrazide) [p, p'-oxybis (benzenesulfonyl hydrazide)], benzenesulfonyl hydrazide ( benzenesulfonyl hydrazide, azobisformamide, azodicarbon amide, dinitroso pentamethylenetetra mine, p-toluenesulfonylhydrazide, p-toluenesulfonylhydrazide Organic blowing agents such as toluenesulfonyl semicarbazide (p-toluene sulfonylsemicarbazide), chlorofluorocarbon blowing agents such as CFCl ₃ , CF ₂ Cl ₂ , ClF ₂ C-CFCl ₂ , HF ₂ CCl, sodium bicarbonate (NaHCO ₃ ) , Ammonium bicarbonate (NH ₄ HCO ₃ ), ammonium carbonate ((NH ₄ ) ₂ CO ₃ ), ammonium nitrite (NH ₄ NO ₂ ), sodium hydrogen borohydride (NaBH ₄ ), Ca (N ₃ ) ₂ (azide compound) Single or plural from inorganic blowing agents such as Process for producing a salt tile having a metal oxide surface layer, characterized in that being.
The method according to claim 8,
The surface coating mixture may further include a dispersant, and the dispersant may be a nonionic surfactant such as fatty acid polyoxyethylene alkyl ether, fatty acid sorbitan ester, fatty acid diethanolamine, alkyl monoglyceryl ether, fatty acid sodium, mono Alkyl sulfate, alkyl polyoxyethylene sulfate, alkylbenzene sulfonate, monoalkyl phosphate, alkyl-2- sulfoxy ethoxy acetamide sodium salt, sodium laureth sulfate, decyl-2- sulfoxy oxy acetamide sodium salt, previously Anionic surfactants such as stil-2-sulfoxyethoxyacetamide sodium salt, palmityl-2-sulfoxyethoxyacetamide sodium salt, stearyl-2-sulfoxyethoxyacetamide sodium salt, dialkyldimethylammonium salt From cationic surfactants such as alkylbenzylmethylammonium salts, amphoteric surfactants such as alkylsulfobetaines, alkylcarboxybetaines Or a process for producing a salt tile having a metal oxide surface layer characterized in that the selection of a plurality.
The method according to claim 8,
The surface coating mixture may further comprise an antifoaming agent, wherein the antifoaming agent is a method for producing a salt oxide tile having a metal oxide surface layer, characterized in that selected solely or a plurality of mineral oil-based antifoaming agent, silicone-based antifoaming agent, polymeric antifoaming agent.
The method according to claim 8,
The dopant is selected from Zr, N, Pt, B, C, F, Al, Ga, In alone or a plurality of methods for producing a salt-generating tile having a metal oxide surface layer.

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