JP2002322389A - Manufacturing method for multifunctional ceramic coating film-forming material curable at low temperature and forming method for multifunctional ceramic coating film curable at low temperature - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for a ceramic coating film-forming material curable at a low temperature, excellent in adhesive strength, heat resistance, chemical resistance, abrasion resistance, durability, water repellency, and the like, capable of decreasing an environmental pollution material and affording a high radiation ratio of far-infrared ray and insulation property and also excellent in bending characteristic. SOLUTION: The multifunctional ceramic coating film-forming material curable at a low temperature is obtained by preparing a mixture solution obtained by adding boric acid, calcium metasilicate, sumectite, kaolin, laponite, ceramics such as magnetite and an oxidized metal to an alkaline silicate, and by mixing therewith a solution obtained by adding a solution of a lithium compound to a solution obtained by reacting an alkali silicate and metal silicon and the like and by adding silicon oxide, titanium dioxide, porcelain fine powder, zirconium oxide, noncrystalline silica oxide or hydrophobic noncrystalline silica oxide to the above mixed solution. The ceramic coating film- forming material is coated to materials except plastics and dried and formed at temperatures suitable for purposes of its use and between a room temperature and 250 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a low-temperature-curable multifunctional ceramic coating material and a method for forming a low-temperature-curable multifunctional ceramic coating material, and to a method for hardening all materials except plastics. Air pollutants and stench,
The effect of reducing or removing sick house syndrome such as aldehydes is remarkable, so that dirt such as oily magic can be removed with water, and a coating film is formed as a multicolored coating material by heating from room temperature to a low temperature. ° High flexural strength, abrasion resistance, corrosion resistance, durability, heat resistance, contamination resistance and water resistance, water repellency, acid resistance, alkali resistance, etc.
A method for producing a low-temperature-curable multifunctional ceramic coating material and a low-temperature-curable multifunctional ceramic coating material, which exhibit many useful physical properties and can be produced and used at low cost without causing pollution. The present invention relates to a method for forming a film.

[0002]

2. Description of the Related Art (1) Conventional organic paints suffer from health damage to workers due to organic solvents at the time of manufacture and painting, and damage due to paint splashing and odors around construction sites, and are flammable. There are many problems such as being strong, causing a fire, and generating toxic gas during a fire, causing serious damage to humans and livestock. In addition, there are many defects such as low surface hardness of the coating film, poor flexibility, stain resistance, acid resistance, and alkali resistance, and the inability to remove stains due to deterioration by ultraviolet rays and oily magic. In order to prevent these physical defects, enamels and glazes for ceramics have been used in some cases. However, these glazes are high energy consumption type for firing at a high temperature of 800 ° C or more, and the substrate material is limited. In addition, the cost of equipment such as glazing equipment and firing equipment is also expensive, and it is difficult to say that it is a coating material for a recycling-based economic society.

(2) Glazes and enamels, which are silicate mixtures,
Generally, it is a homogeneous, amorphous, isotropic, and light-transmissive substance. The melting temperature of such glaze is 600 ° C
In the temperature range from to 2000 ° C., the corresponding chemical compositions are shown in series. Moreover, the temperature of the low fire glaze is 60
0 ° C. is the minimum temperature, and the chemical component at that time generally has a composition containing lead oxide, and the toxicity of the lead compound becomes a problem. As described above, the technology of manufacturing and using a ceramic coating material at a temperature of 600 ° C. or less has not yet been developed, and even more, the method of producing a ceramic coating material at a temperature of around 300 ° C. or less and a method of forming a coating film have not yet been developed. There is no present.

[0004] (3) As a general electric insulating coating agent, an epoxy resin or the like is mixed with an inorganic inorganic powder for insulation, or a glaze which is a thin homogeneous silicate mixture referred to in the ceramic industry is used. Is formed on the surface of the metal or by forming an enamel which is a substance which solidifies into a glass on the metal surface. Among these, the formation temperature of the epoxy resin is 200 ° C. or less. However, an insulating protective film using an organic polymer material has low insulation resistance, and has many weaknesses in durability, heat resistance, etc. There are many problems in occupational health. On the other hand, glazes have good physical properties such as electric insulation and durability, but have a problem such as heat resistance of the material to be bonded because they are formed at a welding temperature of about 800 to 1200 ° C. Are very limited. In addition, high-temperature firing consumes a lot of energy, increases the cost of installing a firing furnace, and increases the load on the environment, resulting in significant environmental impact as heat pollution.

(4) In recent years, low-temperature glazes have been demanded, and Sumiceram, Aron Ceramic, HE
Coating agents such as S, ceramics, cermetel, and TSB are commercially available, but are usually inorganic coating agents that are usually a composite of silica and fluororesin made from a silicone resin. Considering these from the heating temperature, metal alkoxide-high-purity silicon dioxide thin film forming coating agent that requires heating at 450 ° C. or higher, CRM inorganic rust preventive coating agent heated at 200 ° C., and liquid ceramics as a mixture of silanol and siloxane, etc. is there. All of these fall into the category of inorganic paints, and many of them fall within the range of physical properties of organic paints. Among these, a one-part coating agent containing no alkali metal based on a metal alkoxide as an inorganic coating agent is also commercially available. Examples thereof include an electric insulation of 1,000 MQ or more and heat resistance of 1000 ° C.
Although it is said that the temperature is 1500 ° C., a state of peeling often occurs during coating on a material to be bonded, and it is difficult to form a coating film. On the other hand, a metal oxide is added to potassium silicate, which is developed by NASA as an inorganic paint, and aluminum orthophosphate is added to form a potassium phosphate-silicic acid compound.
It is said that there is a film formed by drying at 50 ° C. for 60 minutes, but the examples and characteristics used are not clear.

(5) In recent years, titanium dioxide photocatalysts have been actively used to enhance their functions and to purify the environment. Titanium dioxide used for this, due to the undeveloped adhesive that coats titanium dioxide on various materials, creates titania sol from titanium alkoxide, coats it on a glass substrate etc. by dipping method, then repeats drying and firing,
A titanium dioxide porous pellet is prepared and used based on a sol-gel method. In these methods, the physical properties such as the reduction of the photocatalytic effect due to the transition from anatase-type titanium dioxide to rutile-type titanium dioxide by heating, and the method of forming the coating film limits the selection range such as the type, shape and size of the materials used. In addition to mass production and uniform coatings, the complexity of production and the high price of products limit their spread. This is similar to the fact that there is no development of an efficient and environmentally friendly ceramic coating material that saves energy by using a far-infrared radiation ceramic material that emits light at room temperature. That is, these causes are due to the fact that a suitable inorganic coating material and adhesive have not been developed. On the other hand, in recent years, new low-temperature heating-type paints have come to be marketed, but all of them are inorganic paints, and a solvent is a low molecular organic substance such as alcohol. As a result of testing several inorganic coatings from among these commercial products, it was not possible to achieve the purpose of expressing good physical properties in addition to the convenience in use required in the market, and it was expensive. None of the paints is inadequate. In other words, due to the weakness that adhesive strength and durability are not exhibited unless high temperature treatment is applied and the high price, conventional coatings are not used for general coatings, apart from use in special applications. It is said that there is a tendency to return to organic paints. In short, these facts can be said to be attributable to the fact that inorganic coating materials that are multifunctional and suitable for various purposes have been demanded but have not yet reached the level of development.

[0007]

(1) The ceramic coating material newly developed to solve these defects of the inorganic paint does not contain an organic substance, and the solvent is a coating material depending on the mixing ratio of water. A reaction product is produced at a temperature from room temperature to around 100 ° C under a mechanism that can adjust the solid-liquid ratio and adjust the viscosity of the mixture, and a coating film can be easily formed on materials other than plastics by ordinary methods. After forming the coating film, if it is dried from room temperature to around 110 ° C. or heated to around 250 ° C. according to the purpose of use, heat resistance, chemical resistance, abrasion resistance, durability, etc., and environmental pollution It contributes to the reduction of substances, heating at room temperature or low temperature makes it possible to save energy with high far-infrared radiation and saves energy without environmental pollution.
A method for producing a room-temperature and / or low-temperature curable multifunctional ceramic coating material having excellent properties such as flexibility and a method for forming a coating film are developed. This technology is fundamentally different from conventional organic and inorganic paints containing organic polymers such as organic polymers and oligomers, and water-based paints such as alcohols. Low temperature hardening type multifunctional ceramic coating material which forms ceramic thin film at low temperature from room temperature to around 250 ℃ without high temperature firing like glaze Develop.

(2) The ceramic coating material to be developed is made of alkali silicate as a main component, mixed with metal oxides, ceramic fine powder, etc., so that the network modification and glass formation are performed, and a strong coating film can be formed. A low-temperature-curing multifunctional ceramic coating that forms a compound with a new coating composition between the coating surface and the material to be coated, and provides even stronger adhesion and various physical properties by low-temperature heating We will develop a method for manufacturing materials and a method for forming low-temperature-curable multifunctional ceramic coatings.

[0009] (3) The main raw material of the ceramic coating material to be developed fully utilizes the unused material that is discarded in a large amount from the advanced industry, and the auxiliary raw material is a material that is disposed of by the ceramic industry. In this way, it is possible to lower the price of ordinary organic and inorganic paints, make the conventional coating method and technology fully usable, and to save energy with high adhesive strength and high surface hardness. We will develop a method for producing a thermosetting multifunctional ceramic coating and a method for forming a low-temperature curing multifunctional ceramic coating.

[0010]

The present invention has been intensively studied to solve the above problems and achieve the objects, and as a result, has developed a ceramic coating material which can solve all of these defects. That is, easy to manufacture and use,
All materials except plastic can be used for the substrate, and it has strong adhesive strength in the temperature range from room temperature to 250 ° C. Various materials such as metal oxide or ceramic fine powder are used for the base coating material and the transparent coating material. By blending, it is possible to produce a multifunctional ceramic coating material that exhibits various physical properties such as reduction of pollutants in the air and water, high far-infrared radiation, and electrical insulation. In addition, the shelf life of these ceramic coating materials is long, and the price is less than one third of conventional paints. In addition, unlike conventional organic and inorganic paints, no organic solvent is used and only water is used. Recycling of industrial waste that can be easily collected and recycled by dissolving it easily without dissolving by washing with water or hot water, evaporates from time, etc. are odorless because only moisture is contained in the evaporates. Has developed a new ceramic coating material suitable for an environmental economy and society. That is, the present invention provides a method for producing a low-temperature-curable multifunctional ceramic coating material having the following constitution and a method for forming a low-temperature-curable multifunctional ceramic coating film.

That is, the method for producing a low-temperature-curable multifunctional ceramic coating material according to the present invention comprises the steps of (1) dissolving 100 parts by weight of alkali silicate (sodium silicate or both sodium silicate and potassium silicate) ( Preferably,
After adding a solution (preferably 30 parts by weight of hot water) of 3 to 1 part by weight of boric acid to 50 parts by weight of warm water in the case of sodium silicate No. 1, aluminum hydroxide, calcium metasilicate, sodium aluminate, First, a suspension is prepared by adding 3 to 1 part by weight of each of three or more types of smectite, kaolin, and laponite (preferably, 15 parts by weight of hot water) and, if necessary, 3 to 2 parts by weight of zinc oxide. And 700 to 300 parts by weight of alkali silicate (preferably,
In the case of sodium silicate No. 1, 50 to 30 parts by weight of metal silicon fine powder and 5 to 1 part by weight of aluminum fine powder are added to 100 parts by weight of warm water to 500 to 400 parts by weight, In the second step of adding 10 to 0.5 parts by weight of the lithium compound to the reaction solution obtained in the range of 0 ° C. to form a reaction solution, the second step is performed with respect to 60 to 30 parts by weight of the solution obtained in the first step. After mixing 70 to 40 parts by weight of the solution obtained in the two steps, the mixed solution is mixed with at least one of 80 to 90% of one or more of silicon dioxide, ceramic or porcelain fine powder, zirconium oxide, titanium dioxide, and magnetite fine powder.
A third step of adding and kneading 20 parts by weight, and after applying the mixed solution obtained in the third step to the material to be coated, from room temperature to 2
Drying at a temperature range of about 50 ° C, heating and curing.
A method for producing a low-temperature-curable multifunctional ceramic coating material and a method for forming a low-temperature-curable multifunctional ceramic coating film, which are characterized by comprising steps, were developed.

(2) Metal silicon fine powder 50 to 3 is added to an aqueous solution in which 700 to 300 parts by weight of alkali silicate is dissolved.
0 parts by weight and, if necessary, 5 to 1 parts by weight of aluminum fine powder to 100 parts by weight of the reaction solution obtained in the range from room temperature to 100 ° C. The first step of a transparent coating material prepared by dissolving 8 to 1% of fine powder of hydrophilic amorphous silicon dioxide in an aqueous solution prepared by adding 5 parts by weight, and 100 parts by weight of alkali silicate were dissolved. After adding a solution of 3 to 1 part by weight of boric acid to the aqueous solution, aluminum hydroxide, calcium metasilicate,
A second step of adding 3 to 1 part by weight of each of three or more of sodium aluminate, smectite, kaolin, and laponite, and adding 3 to 2 parts by weight of zinc oxide as needed to form a suspension, and a first step 80 ~ of the transparent coating material obtained in
A mixed solution obtained by mixing 40 parts by weight and 60 to 20 parts by weight of the suspension obtained in the second step is mixed with at least one of silicon dioxide, fine powder of ceramics or porcelain, zirconium oxide, titanium dioxide, and fine powder of magnetite. A third step of adding 80 to 20 parts by weight and further adding 6 to 1 part by weight of a hydrophobic amorphous silicon dioxide compound and kneading to form a mixed solution; A fourth step of drying, heating and curing at room temperature and / or a temperature range of 210 ° C. after applying the non-conductive coating material to the material to be coated. A method for producing a low-temperature-curable multifunctional ceramic coating having water repellency and a method for forming a low-temperature-curable multifunctional ceramic coating have been developed.

Next, an outline of an action mechanism such as a reaction between the respective components used in the present invention will be described. (1) The aqueous sodium silicate solution becomes more colloidal as the ratio of silicic acid to sodium oxide becomes 2 or more.
When the ratio of silicic acid to sodium silicate is less than 1, silicic acid exists as monosilicic acid, and when the ratio is higher than this, polysilicic acid exists, and the ratio of silicic acid to sodium oxide is relatively less than 3. In an aqueous sodium silicate solution, if the hydrogen ion concentration is 10.5 or more, it will exist as monosilicate ions. Looking at these states with respect to the distribution of the silicate anion in the aqueous sodium silicate solution, Na /
As the Si ratio decreases, SiO ₄ , Si ₂ O ₇ , S
The amount of i ₃ O ₁₀ decreases and the amount of polysilicic acid increases. In addition, a solution having a high concentration of monosilicic acid gels when the solution is left at a different hydrogen ion concentration. Therefore, the time to gelation could be regarded as a measure of the speed of polymerization of silicic acid. On the other hand, the critical concentration of gelling silicic acid is the lowest when the hydrogen ion concentration is around 7, and slightly differs between sodium silicate and potassium silicate solutions, but increases sharply toward the alkali side. For the effect of temperature,
At high temperatures, the solubility of amorphous silica is high, so the degree of supersaturation of monosilicate ions decreases, and the growth rate of polysilicate particles increases with temperature. On the other hand, when gelation occurs due to a high concentration of silicic acid, the gelation time decreases as the temperature increases, but when the hydrogen ion concentration is around 10.5 or higher, the gelation time increases with the increase in temperature, but the gelation time decreases below that. The gelation time becomes shorter at the hydrogen ion concentration. In this way, the alkali silicate aqueous solution takes various forms depending on the concentration and temperature,
At present, it may not be fully understood including the effects of the polymerization process and coexisting salts.

(2) In the step of adding the aqueous solution of boric acid to the aqueous solution of alkali silicate according to claims 1 and 2, when the concentration of the aqueous solution of boric acid is low, the speed of polymerization of monosilicic acid is not affected so much. In state. Therefore, when the alkali silicate is sodium silicate No. 1,
With the addition of 50 parts by weight of warm water to 100 parts by weight, the presence of monosilicate ions at a hydrogen ion concentration of about 10.5, aluminum hydroxide, calcium metasilicate, sodium aluminate, smectite, kaolin, and laponite By adding 3 to 1 part by weight of each of the above and, if necessary, adding 3 to 2 parts by weight of zinc oxide to form a suspension, an increase in adhesiveness and surface hardness is exhibited. The aluminum hydroxide and sodium aluminate added at this time contribute to the curing agent, and calcium metasilicate and kaolin contribute to the development of the physical properties of the coating film as the aggregate. On the other hand, by dispersing smectite and laponite in water, the replaceable alkali ions of the aqueous alkali silicate solution are hydrated to form colloidal dispersion. In these dilute materials, the repulsion between the particles does not occur and the viscosity does not increase in a dilute solution because the surface charge is much larger than the small end charge.
This dispersed state is a sol, and this state is produced in the production of a ceramic coating material, and kaolin is blended as necessary to adjust the viscosity in such a diluted state of the solution. The mixing ratio of these compounding materials is determined by experiments, and the mixing ratio is as described in claim 1. Smectite and laponite disperse in water but do not disperse in organic solvents. When a large amount of an ionic organic compound is present, flocculation may occur, so the use of an organic surfactant or the like is not desirable.
This is because the dissociable cation association occurs before dispersion occurs only in water. The crosslinked structure of these compounds results in excellent suspension stability properties that prevent sedimentation, rather than slowing down sedimentation due to increased viscosity, and this crosslinking also creates a thickening effect. With respect to this viscosity, an appropriate viscosity range is set according to the coating film forming method, and an appropriate mixing ratio of the compounding material is sufficiently achieved within the scope of claims 1 and 2. In other words, as a result of experiments, it was found that the mechanism of action and the quantitative ratio for the formation of a compounding material and a curing agent and a colloidal sol, and for the adjustment of the viscosity, which were properly applied to the development of physical properties by drying and heating of this coating film, were determined as a result of the experiment. In the material, the range of 3 to 1 part by weight of the compounding material is appropriate for 100 parts by weight of the alkali silicate. Zinc oxide is added in order to form a cured product by strong crosslinking with silicate when heating at a medium / high temperature is required. Generally, the molecular formula of zinc oxide is ZnO, but zinc oxide is ZnO _{1 + δ} , so that zinc is extra by δ with respect to oxygen, but this is also due to the defect of oxygen atoms on the crystal lattice. Although it is not clear whether zinc atoms are excessively interspersed between lattices, it is clear from the experimental results of coating film formation that the role of the network modifying component as a bridging effect is performed together with heating. I have. From these experimental results, the quantitative range of the film-forming components was selected from the above experimental results.

(3) In the case where sodium silicate and potassium silicate are used as the alkali silicate, when the sodium silicate is only sodium silicate, 50% of sodium silicate is used.
0 to 300 parts by weight is used. In the case of mixing sodium silicate and potassium silicate, 500 to 300 parts by weight of potassium silicate is used for 100 parts by weight of sodium silicate. That is, the weight ratio is in the range of 5-3: 0 parts by weight and 1: 5-3. On the other hand, 50 to 30 parts by weight of the metal silicon fine powder and 5 to 1 part by weight of the aluminum fine powder are used.
A coating solution is prepared by blending 10 to 0.5 parts by weight of a lithium compound with a reaction solution obtained by blending a range of parts by weight. Here, the reaction between the aqueous alkali silicate solution and metallic silicon will be described. That is, all forms of metallic silicon react with and dissolve in the aqueous alkali silicate solution. This is because metallic silicon reacts with an alkaline aqueous solution and dissolves in water by the catalysis of OH ⁻ by the reaction of SiO ₄ ^4- and Si (OH). The lithium ion for causing a cross-linking reaction to such a silicate tetrahedron or silanol group and aluminum hydroxide or zinc oxide as a curing agent for the suspension produced in the first step are blended and then dried and heated. By the polycondensation, a strong silica gel is formed on the material to be coated. At the same time, silicon dioxide, fine powder of porcelain, zirconium oxide, titanium dioxide and magnetite fine powder mixed in the base coating material are present in the surface layer of the coating when forming the coating, thereby reducing durability and contaminants. In addition, high electrical insulation characteristics and far-infrared emissivity are also exhibited, and a strong coating film is formed. From these results, the blending range of the coating film material is a numerical value in which a certain range is selected from many experimental results.

(4) The step of adding a metal silicon fine powder and an aluminum fine powder to an alkali silicate to form a reaction solution comprises dissolving both the metal silicon and the aluminum fine powder in an alkali to form a silica-rich Al-Si. Form a sol of alkali salt. The sol-like basic coating material in which a lithium compound is dissolved in this aqueous solution is heated by applying the basic coating material to the material to be coated due to the presence of lithium having an ion radius slightly smaller than that of sodium or potassium. For example, aluminum as a gel-like glass-forming product and lithium as a network modifier contribute to vitrification by heating, and a durable coating film can be formed. According to experiments, the amount of the lithium compound added is in the range of 10 to 0.5 parts by weight based on 100 parts by weight of the alkali silicate, for example, 10 to 3 parts by weight in the case of lithium hydroxide, and 1 to 0 part by weight of lithium carbonate. .5
It is determined that the blending of parts by weight is appropriate.

(5) The particle size of the silicon dioxide used in the first and second aspects is 0.2 μm or less in order to increase the content of the silicon dioxide in the coating material and improve the electrical insulation properties. Is selected, and the particle size of the crushed fine particles of the porcelain is 2 microns or less. As a result, it is desired that the compounded material which greatly contributes to the electric insulation property is desirably fine and spherical silicon dioxide. That is, from the measurement results, it is appropriate that the compounding ratio of silicon dioxide is 70 to 50 parts by weight based on 100 parts by weight of the base coating material. However, when the fine powder of the fine porcelain is mixed, the particle size is preferably set to 2 microns or less, and the mixing ratio of silicon dioxide is preferably about 40 to 20%.

(6) In order to increase the amount of silica sol in the solution by adding amorphous silicon dioxide, the hydrogen ion concentration of the aqueous solution is desirably 10 or more. In this case, the solubility rapidly increases and silicate ions are generated. . Therefore, 8 to 1% of this fine amorphous silicon dioxide is blended to form a transparent coating material, and further, various kinds of metal oxides and ceramic fine powders are mixed with the transparent coating material to form silicon dioxide. To produce a low-temperature-curable multifunctional ceramic coating material with excellent physical properties.

(7) The method for forming a sufficiently thick coating film is based on the base coating material which is a mixed solution of the suspension obtained in the first step and the reaction solution obtained in the second step. A mixed solution containing at least one compatible amount of silicon dioxide, ceramic or porcelain fine powder, zirconium oxide, titanium dioxide, and magnetic iron fine powder, ie, the suspension obtained in the first step and the mixed solution in the second step. After applying the obtained mixed solution to the material to be coated and drying it sufficiently at around 100 ° C., the operation of applying the mixed solution again to the dried surface is repeated several times,
If the film is heated at a predetermined temperature during this period, a strong film having a thickness of about 100 microns can be formed. In this case, in order for the suspension to adhere, it is possible to adhere because the surface energy of the coating film surface of the former stage is again or again less than the surface energy when applied and dried.
Therefore, the operation of applying the mixed solution to the sufficiently dried surface by repeating the drying for each application is performed. In this case, an operation of applying a coating material having a difference in surface energy of the coating film is performed. For that purpose, it is necessary to consider the appropriate selection of the type and the amount of the compounding material to be mixed with the reaction solution obtained in the second step. In this way, when a thick coating is required, the surface energy of the coating material of the coating material to be overlaid is made several types of coating materials having a small surface energy as it extends from the lower layer to the upper layer, and is sequentially applied. It is desired to form a coating film. In this case, the surface hardness of the coating film decreases as the number of times of application increases, as compared with the case where the coating is applied once. However, if a coating film is formed in this way, 1
It is possible to form a thick coating film of about 00 microns.

(7) In the processing method for forming a sufficiently thick coating film according to claim 2, the type and the mixing ratio of the compounding materials to be mixed with the transparent coating film material obtained in the first step of claim 2 are appropriately adjusted. To make several kinds of different coating materials, mix each coating material with the appropriate amount of the suspension obtained in the second step,
After repeating the drying each time these different mixed solutions are applied, and heating at a predetermined temperature up to around 210 ° C., several tens to one having good water repellency and various physical properties are obtained.
It is possible to arbitrarily form a surface coating film having a thickness of about 00 microns.

(8) To form a thick surface coating film, an appropriate amount of the suspension obtained in the second step is mixed with the transparent coating material obtained in the first step in claim 2, and In order to express the physical properties of the coating film according to the purpose of the mixed solution prepared in the third step by adding and kneading the hydrophobic silicon dioxide compound to the suspension, the type and compounding of the compounding material added in the second step Depending on the appropriate selection of the ratio, several types of coating materials thus formed are formed as coating films on the material to be coated, and the film thickness is to be applied while the coating film is not sufficiently dried. The method of forming the film is selected, and a film having excellent water repellency and a film thickness of about 100 μm are formed by layering with the film material by heating at room temperature and / or any temperature up to around 210 ° C. Can be.

Here, the reasons for limiting the respective numerical ranges according to the constitution of the present invention will be described. However, the compounding ratios of the compounding materials of the low-temperature curing type multifunctional ceramic coating material are mutually related. However, it is difficult to strictly limit the mixing ratio. (1) Generally, in the first step of claim 1, when the alkali silicate is JIS No. 1 sodium silicate, 60 to 40 parts by weight of deionized water heated with respect to 100 parts by weight of sodium silicate 1 is added. A hydrolyzed aqueous solution is prepared by pouring, and a solution obtained by pouring 40 to 30 parts by weight of warm water into 3 to 1 part by weight of boric acid is added to the aqueous solution to form a sol of silicic acid. In this case, if the amount of deionized water heated to JIS No. 1 sodium silicate is small, it is difficult to form a sufficient sol of silicic acid when a solution of boric acid is added. If a large amount of deionized water is added to the material, the adhesive strength to the material to be coated is eventually reduced. The amount of each compounding material to be added to the aqueous solution thus prepared is 3
-1 part by weight, the viscosity (CP) of this suspension is 700-
In the range of about 1,300, it was confirmed that these suspensions were suitable for coating by brushing or spraying. In this case, if the amount of each compounding material is larger than this, the viscosity of the suspension is so high that it is difficult to form a coating film, and moreover, the coating film often has defects such as cracks. On the other hand, when the amount of each compounding material is smaller than this, cracks occur in the dried coating film and the surface hardness decreases. Therefore, it can be seen that the amounts of various compounding materials to be compounded have an appropriate compounding ratio range. Claim 1
The quantitative relationship of these compounded materials shown in claim 2 is based on comprehensive judgment of the results of repeated experiments.

(2) In the second step, the alkali silicate is sodium silicate No. 1, and its weight ratio is 5 to 3
In the case of parts by weight and in the case of sodium silicate No. 1 and potassium silicate solution, the weight ratio is 1: 3 and 50 parts of hot water is used.
The specific gravity of the reaction solution prepared by adding 50 to 30 parts by weight of the metal silicon fine powder to the solution to which 0 to 400 parts by weight is added is in the range of 1.01 to 1.05, and the lithium compound is blended and dissolved. It is a suitable concentration. When the weight ratio of the sodium silicate No. 1 is less than 5 to 3, unreacted silicon remains with respect to the amount of the metal silicon fine powder, and when the weight ratio is large, a large amount of sodium hydroxide exists in the solution, so that the coating is performed. The film material dissolves in moisture. Therefore,
The compounding ratio of the alkali silicate and the metal silicon is defined in this range, and the compounding ratio and the quantitative relationship of these compounding materials are ultimately determined by comprehensive judgment of the experimental results.

(3) In the reaction of the alkali silicate and the metal silicon fine powder according to claim 2, a hydrophilic amorphous silicon dioxide is added to an aqueous solution prepared by adding a fine aluminum powder, if necessary, and then compounding a lithium compound. 8-1 fine powder
% And dissolved to form a transparent coating material. When the compounding ratio of the fine powder of the hydrophilic amorphous silicon dioxide is smaller than this numerical range, the drying speed of the coating film and the surface hardness of the coating film are small because the silicate sol of the transparent coating material is small. Become
If it exceeds this range, the hydrogen ion concentration of the transparent coating material decreases, and the material does not form a sol. Such a mixing ratio and a quantitative relationship of the transparent coating material are ultimately based on a comprehensive judgment of the experimental results.

(4) The method according to claim 2, wherein 6 to 1 parts by weight of a fine powder of a hydrophobic amorphous silicon dioxide compound is added to the suspension obtained in the second step and kneaded, or Various properties are added to the transparent coating material obtained in the above, and further 6 to 1 parts by weight of a hydrophobic amorphous silicon dioxide compound is added and kneaded, and the physical properties of the coating film are set to a room temperature curing type. Exhibits high water repellency and high surface hardness. At this time, if the blending ratio of the hydrophobic amorphous silicon dioxide compound is smaller than 1, sufficient water repellency is not exhibited, and if the blending ratio is larger than 6, the viscosity increases, and the viscosity is increased in the second step. A mixed solution obtained by adding various compounding materials to a suspension or a transparent coating material cannot be mixed and kneaded with a usual kneading apparatus or stirring apparatus. Moreover,
If it forms in this way, a coating material will show a lump and a coating film formation will be impossible. As described above, the mixing ratio and the quantitative relationship of the compounding materials are finally based on comprehensive judgment of the experimental results.

(3) The compounding ratio of the compounding materials set forth in claims 1 and 2 is such that an appropriate viscosity and specific gravity range are ensured, and the coating film is formed by a general coating film forming apparatus when forming the coating film. This is a numerical range in which a range in which the film can be formed and cured at room temperature and / or low temperature to exhibit the desired coating film physical properties is selected. Regarding the limitation of each of these numerical ranges, the blending ratio of each blended material of the low-temperature curing type multifunctional ceramic coating material is originally related to each other, and it is difficult to strictly define the strict blending ratio. However, the compounding ratio and the quantitative relationship of such compounding materials were ultimately comprehensively determined from many experimental results. And the formation of a coating film becomes difficult. In this way, the coating material made by proper blending ensures certain high physical properties by heating at room temperature and / or low temperature,
In addition, there is no multi-functional ceramic coating material which is pollution-free, energy-saving and has a very low environmental load, in which the product price is as low as one-third of the price of ready-made paints.

[0027]

Next, a method for producing a low-temperature curing type multifunctional ceramic coating material and a method for forming a coating film according to the present invention will be described.
This will be specifically described with reference to examples. Example 1 A solution of 2 parts by weight of boric acid was added to an aqueous solution in which 100 parts by weight of sodium silicate had been dissolved, and then aluminum hydroxide, smectite, and kaolin were added in 1 part each.
A first step of preparing a suspension by adding parts by weight, and adding 40 parts by weight of metal silicon fine powder and 3 parts by weight of aluminum fine powder to 200 parts by weight of sodium silicate and 300 parts by weight of potassium silicate, and adding the mixture to a temperature of from room temperature to 100 ° C. In the second step of the aqueous solution prepared by adding 3 parts by weight of lithium hydroxide to 100 parts by weight of the reaction solution obtained in the above range, 50 parts by weight of the solution obtained in the first step is added. After mixing 50 parts by weight of the solution obtained in the second step, the mixed solution was used as a base coating material, and 50 parts by weight of silicon dioxide and 50 parts by weight of zirconium oxide fine powder were added to the base coating material. In the third step of kneading, and after applying the mixed solution obtained in the third step to the material to be coated with a spray gun and drying, the coating is applied in the fourth step of heating at 250 ° C. for 10 minutes. Let it form The physical properties of the coating film was measured. The results are shown in Table 1.

[0028]

[Table 1]

Example 2 A solution of 2 parts by weight of boric acid was added to an aqueous solution in which 100 parts by weight of sodium silicate was dissolved, and then 2 parts by weight of each of aluminum hydroxide, calcium metasilicate, smectite, and kaolin were added. A first step of preparing a suspension by adding 30 parts by weight of metal silicon fine powder to 300 parts by weight of sodium silicate and 200 parts by weight of potassium silicate to form a reaction solution obtained in a temperature range from room temperature to 100 ° C. A second reaction solution is prepared by adding 3 parts by weight of a lithium compound to 100 parts by weight of the reaction solution.
In the step, after mixing 700 parts by weight of the solution obtained in the second step with 300 parts by weight of the solution obtained in the first step, 0.2 μm or less is mixed with 100 parts by weight of the mixed solution. A coating material obtained by mixing 60 parts by weight of silicon dioxide having a spherical shape is applied to a material to be coated with a spray gun, the film thickness is adjusted to about 20 μm, and drying is performed. For 10 minutes to form a coating film, and the electrical insulation resistance and various physical properties of the coating film were measured. The results are shown in Table 2.

[0030]

[Table 2]

Example 3 40 parts by weight of metal silicon fine powder and 3 parts by weight of aluminum fine powder were added to 300 parts by weight of sodium silicate and 300 parts by weight of potassium silicate, and a reaction solution obtained in a temperature range from room temperature to 100 ° C. was obtained. First step of transparent coating material made by dissolving 2% of fine powder of hydrophilic amorphous silicon dioxide in an aqueous solution made by adding 3 parts by weight of lithium hydroxide to 100 parts by weight of this reaction solution And boric acid 2 in an aqueous solution in which 100 parts by weight of sodium silicate are dissolved.
After the addition of 1 part by weight of the solution, 1 part by weight of each of aluminum hydroxide, sodium aluminate, smectite and kaolin is added to form a suspension, and the transparency obtained in the first step is obtained. To a mixed solution obtained by mixing 60 parts by weight of the coating material and 40 parts by weight of the suspension obtained in the second step, 50 to 20 parts by weight of fine particles of anatase-type titanium dioxide were added to form a coating material. After applying the obtained low temperature curing type ceramic coating material to the material to be coated with a spray gun, adjusting the film thickness to about 10 μm, and performing drying,
After heating at 210 ° C. for 10 minutes to form a coating film, the reduction rate of acetaldehyde and the reduction rate of nitric oxide were measured as photocatalysis. The results are shown in Tables 3 and 4.
Shown in

[0032]

[Table 3]

[0033]

[Table 4]

Example 4 After a solution of 2 parts by weight of boric acid was added to an aqueous solution in which 100 parts by weight of sodium silicate was dissolved, 2 parts by weight of each of aluminum hydroxide, calcium metasilicate, smectite, and kaolin were added. A first step of preparing a suspension by adding 30 parts by weight of metal silicon fine powder to 300 parts by weight of sodium silicate and 200 parts by weight of potassium silicate to form a reaction solution obtained in a temperature range from room temperature to 100 ° C. A second reaction solution is prepared by mixing 3 parts by weight of lithium hydroxide with 100 parts by weight of the reaction solution.
In the step, 700 parts by weight of the solution obtained in the second step is mixed with 300 parts by weight of the solution obtained in the first step, and 50 parts of the fine ceramic powder is mixed with 100 parts by weight of the mixed solution. % And 20% of the magnetite fine powder are applied to the material to be coated with a spray gun to a film thickness of about 30 μm and dried, and then heated at a temperature of 180 ° C. for 10 minutes. After forming the coating, the emissivity of the far-infrared radiator was measured at a heating temperature of 500 ° C. in comparison with a perfect black body. The results are shown in FIGS.

Example 5: In the first step, 20 parts by weight of warm water and 500 parts by weight of potassium silicate, 40 parts by weight of metal silicon fine powder and 2 parts by weight of aluminum fine powder were added to 100 parts by weight of sodium silicate, A reaction solution is prepared at a temperature in the range from to 100 ° C. To 100 parts by weight of this reaction solution, 3 parts by weight of lithium hydroxide was added to form an aqueous solution, and 2% of hydrophilic amorphous silicon dioxide fine powder was dissolved in this aqueous solution to form a transparent coating film. Make wood. On the other hand, in the second step, a solution of 2 parts by weight of boric acid was prepared in an aqueous solution in which 100 parts by weight of sodium silicate was dissolved, and three kinds of compounding materials of aluminum hydroxide, sodium aluminate, and kaolin were added to the solution. Add suspension by weight. Next, as a third step, 70 parts by weight of the transparent coating material obtained in the first step and 30 parts of the suspension obtained in the second step are used.
Parts by weight are mixed to form a mixed solution. To this mixed solution, 40 parts by weight of zirconium oxide powder is added, and 3 parts by weight of a hydrophobic amorphous silicon dioxide compound is further added and kneaded to form a mixed solution. The coating material obtained in the third step was applied to the material to be coated by spraying, and then dried and cured at room temperature to form a water-repellent, room temperature-curable coating film. The results are shown in Table 5.

[0036]

[Table 5]

[0037]

As described in the above embodiments, according to the present invention, in addition to the following excellent effects, a low-cost, non-polluting and recycling-based society using industrial waste as a raw material is formed. A new method for producing a low-temperature-curable multifunctional ceramic coating material and a method for forming a low-temperature-curable multifunctional ceramic coating film that contribute to propulsion have been developed. That is, (1) the conventional organic paint has many problems such as causing health damage and inflammability, causing a fire, and generating toxic gas at the time of the fire, causing serious damage to humans and livestock. In addition, the surface hardness of the coating film is small, the flexibility, the stain resistance, the acid resistance and the alkali resistance are poor, and there are many defects such as deterioration and contamination. To prevent these, enamel and ceramic glaze have been used.
The substrate material is limited to a high energy consumption type for firing at a high temperature of 0 ° C. or higher. Furthermore, equipment costs such as a glaze apparatus and a baking apparatus are expensive, and it is hard to say that this is a coating material for a recycling-based economic society. On the other hand, an organic polymer or an organic-inorganic composite material has been used as an electric insulator material, but there are many difficulties in terms of a coating film forming operation, performance, and cost. As a result of developing a low-temperature-curable ceramic coating material to eliminate all of these defects, as shown in Examples 1, 2, and 5, the surface hardness of general paints was reduced by pencil strength. The surface hardness of the coating film developed according to the present invention is about
The hardness is as high as about 5 and 180 degrees or less is exhibited at about 5 microns or less. Further, in this coating film formation, low temperature heating of a maximum heating temperature of 250 ° C. and a holding time at a predetermined temperature of about 10 to 20 minutes is sufficient, and depending on the purpose of use, high water repellency, durability and the like are obtained by drying at room temperature. Expression of various physical properties can be obtained. In this way, organic polymer paints and organic-inorganic composite paints, which have been used in the past, are fundamentally revolutionized. They are pollution-free, energy-saving, water-repellent, and durable. We have developed a method for producing a low-temperature-curable multifunctional ceramic coating material and a method for forming a low-temperature-curable multifunctional ceramic coating material that can be supplied at a price lower than one-third.

(2) The application of titanium dioxide photocatalysts to high functionality and environmental purification is being actively pursued. When coating titanium dioxide for various materials, the performance is reduced due to the adhesion of titanium sol by heating, and the selection range of material type, shape, size, etc. is narrow, and mass production and uniformity In addition, the spread is limited due to the complexity of manufacturing and high price. As shown in Tables 3 and 4, these bottlenecks are eliminated and the removal of sick house syndrome and the reduction of air pollutants can be performed in a short time with high efficiency by the usual coating film forming method. We have developed a photocatalytic ceramic coating material of titanium dioxide and a method of forming the coating film, which can be sold for less than one tenth of the price of the product.

(3) At present, no room temperature or low temperature hardening type far-infrared radiation ceramic body which saves energy and does not burden the environment has been developed. That is, these causes are due to the fact that a suitable inorganic coating material and adhesive have not been developed. In recent years, new low-temperature heating paints have been marketed, but all of them are inorganic paints and use low molecular organic substances such as alcohols as solvents. As a result of testing some of these commercially available paints called inorganic paints, it is far from the purpose of expressing advanced physical properties in addition to the ease of use required in the market, and it is expensive. However, all of the paints are insufficient. Therefore, far-infrared radiators are generally used today by welding using ceramics obtained by high-temperature treatment because of their weaknesses such as poor adhesive strength, durability and heat resistance and high price. In short, this can be said to be attributable to the fact that, despite the demand for a multifunctional and multipurpose inorganic coating material, it has not yet reached the level of development. As shown in Example 4 and FIGS. 1 and 2, the emissivity of the infrared emitting ceramic body to be developed is 0.9 or more, and the emissivity of the far infrared emitting ceramic currently used is 0.8. By comparison, it is clear that the efficiency is remarkably high and a stable emissivity is exhibited in all wavelength ranges. In addition, this radiator can form a coating on any material having an arbitrary shape and size except for a plastic material, and the coating is formed by drying at room temperature or heating to around 250 ° C. After forming and manufacturing the film with a thickness of 30 μm or less, the operating temperature is 8 μm.
This is a new far-infrared radiation ceramic coating material that can withstand heating up to around 00 ° C and develops a high emissivity. .

(3) Main raw materials are metallic silicon and ceramic waste discharged from advanced industries. The low-temperature-curable multifunctional ceramic coating material developed in this study is a technology that makes full use of these wastes, and the solvent used for the coating material is water, which saves resources. It is an energy-saving and pollution-free product that is linked to the creation of a new industry in the new 21st century recycling-oriented economy.

(4) In forming a coating film, a usual method for applying an organic paint and a working machine / equipment can be used as they are, and since the solvent is water, it is odorless at the time of manufacturing and working, so that a working place is required. It is an environmentally friendly low temperature curing type multifunctional ceramic coating material that can be selected.

(5) This low-temperature-curable multifunctional ceramic coating material has an average coating thickness of 30 microns.
At least 4-5 m ² per kg of coating material
The formation area of this coating film includes the amount of scattered paint at the time of forming the coating film. On the other hand, the average price of these various coating materials is extremely lower than one-third of the price of conventionally available organic paints and adhesives, and the safe storage period of these coating materials is one month. Years or more are guaranteed. In addition, the container for storing and using the coating material is made of plastic, and when reused, it can be easily washed by washing with water or hot water, so the container can be reused any number of times. It will be the most suitable product.

[0043]

[Brief description of the drawings]

FIG. 1 is a diagram of far-infrared emissivity of two types of coating films in which chamotte is blended with a base coating material. (Example 4)

FIG. 2 is a diagram of far-infrared emissivity of two types of coating films in which chamotte and magnetite fine powder are blended into a base coating material. (Example 4)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B05D 7/24 303 B05D 7/24 303B 303C 303D C09D 5/16 C09D 5/16 F term (Reference) 4D075 BB21Z BB24Z BB26Z CA02 CA03 CA13 CA18 CA34 CA36 CA44 EA06 EA10 EA19 EB01 EB02 EB05 EC01 EC02 EC05 4J038 AA011 HA061 HA171 HA211 HA241 HA431 HA451 HA471 HA521 HA551 HA561 NA03 NA04 NA05 NA07 NA11 NA14 PA19 PC03

Claims (11)

[Claims] 1. A solution of 3 to 1 part by weight of boric acid is added to an aqueous solution in which 100 parts by weight of alkali silicate is dissolved, and then aluminum hydroxide, calcium metasilicate, sodium aluminate, smectite, kaolin and laponite are added. A first step of adding 3 to 1 part by weight of each of three or more types and, if necessary, adding 3 to 2 parts by weight of zinc oxide to form a suspension; and an aqueous solution in which 700 to 300 parts by weight of an alkali silicate is dissolved. 50 to 30 parts by weight of a metal silicon fine powder and, if necessary, 5 to 1 part by weight of an aluminum fine powder to obtain 100 parts of a reaction solution obtained in a temperature range from room temperature to 100 degrees Celsius.
If necessary, 10 to 10 parts by weight of lithium compound
In the second step of the aqueous solution prepared by adding 0.5 parts by weight, 70 to 40 parts by weight of the solution obtained in the second step are mixed with 60 to 30 parts by weight of the solution obtained in the first step. The mixed solution is used as a base coating material, and at least one of silicon dioxide, fine powder of ceramic or porcelain, zirconium oxide, titanium dioxide, and magnetite fine powder is added to the base coating material.
A third step of adding and mixing by 20 to 20 parts by weight, and a fourth step of applying the mixed solution obtained in the third step to the material to be coated, drying and heating at room temperature to a temperature of 250 degrees Celsius to cure.
A method for producing a low-temperature-curable multifunctional ceramic coating film and a method for forming a low-temperature-curable multifunctional ceramic coating film, comprising: 2. An aqueous solution in which 700 to 300 parts by weight of an alkali silicate is dissolved, 50 to 30 parts by weight of metal silicon fine powder and, if necessary, 5 to 1 part by weight of aluminum fine powder are added, and the temperature is changed from room temperature to 100 ° C. An aqueous solution prepared by adding 10 to 0.5 parts by weight of a lithium compound to 100 parts by weight of the reaction solution obtained in % Of a transparent coating material produced by dissolving 3 parts by weight of boric acid in an aqueous solution of 100 parts by weight of alkali silicate, and then adding aluminum hydroxide, calcium metasilicate,
A second step of adding 3 to 1 part by weight of each of three or more of sodium aluminate, smectite, kaolin, and laponite, and adding 3 to 2 parts by weight of zinc oxide as needed to form a suspension, and a first step 80 ~ of the transparent coating material obtained in
One or more types of silicon dioxide, ceramic or porcelain fine powder, zirconium oxide, titanium dioxide, and magnetite fine powder are added to a mixed solution obtained by mixing 40 parts by weight and 60 to 20 parts by weight of the suspension obtained in the second step. A third step of adding 80 to 20 parts by weight, further adding 6 to 1 part by weight of a hydrophobic amorphous silicon dioxide compound fine powder and kneading to form a mixed solution, and a low-temperature curing type obtained in the third step A low-temperature curing type having water repellency, which comprises a fourth step of applying the multifunctional coating material to the material to be coated, drying and heating at room temperature to 210 degrees Celsius and curing. A method for producing a multifunctional ceramic coating material and a method for forming a low-temperature curing type multifunctional ceramic coating film. 3. The alkali silicate is sodium silicate or both sodium silicate and potassium silicate. In the case of sodium silicate and potassium silicate, their weight ratio is 5 to 3: 0 parts by weight or 1: 5 to 5 parts by weight. 3. The method according to claim 1, wherein the amount is 3 parts by weight. 4. The low-temperature-curable multifunctional ceramic coating material according to claim 1, wherein the lithium compound is lithium hydroxide or lithium carbonate or both lithium hydroxide and lithium carbonate. Manufacturing method. 5. The ceramic fine powder is a chamotte containing as much iron compound as possible, and the porcelain fine powder is a shelven having a composition of a fine porcelain, and their particle size is preferably less than 2 microns. 3. The method for producing a low-temperature-curable multifunctional ceramic coating material according to claim 1 or claim 2. 6. The crystal form of titanium dioxide to be blended with a basic coating material for the purpose of reducing harmful substances, deodorizing, sterilizing, etc. is mostly anatase-type fine particles, and the coating material emits ultraviolet rays. 3. The method for producing a low-temperature-curable multifunctional ceramic coating material according to claim 1, wherein the crystal form of the titanium dioxide when used for the purpose of protection is mostly rutile. . 7. In the fine powder of hydrophilic silicon dioxide,
3. The low-temperature-curable multifunctional ceramic according to claim 2, wherein the average particle size is about several tens of nanometers, and further, it is amorphous, has high dispersibility, and has a hydroxyl group in a side chain. Manufacturing method of coating material. 8. The fine powder of the hydrophobic silicon dioxide compound has an average particle size of about several tens of nanometers and has an alkyl group in a side chain, and the alkyl group in the side chain is usually a methyl group. 3. The method for producing a low-temperature-curable multifunctional ceramic coating material according to claim 2, comprising: 9. A method for forming a sufficiently thick coating film is to apply a multifunctional ceramic coating material to a material to be coated by an ordinary method, dry the coating material sufficiently, and then apply the ceramic coating material again. 2. The low-temperature-curing multifunctional composition according to claim 1, wherein after a coating operation on the surface is repeated several times, the coating is dried and heated sufficiently to obtain a coating thickness of about 100 microns. A method for forming a ceramic coating. 10. With respect to a ceramic coating material containing a hydrophobic silicon dioxide compound, a method for forming a sufficiently thick coating film is to form a coating film on a material to be coated to a thickness of several tens of microns by an ordinary method. After repeatedly forming a coating film having a thickness of several tens of microns again while not drying sufficiently, drying and heating to obtain a coating film thickness of about 100 microns. Item 10. A method for forming a low-temperature curing type multifunctional ceramic coating film containing the hydrophobic silicon dioxide compound according to item 2. 11. A method of forming a sufficiently thick coating film according to claim 1, wherein the low-temperature-curable multifunctional ceramic coating material according to claim 1 is repeatedly formed and dried sufficiently, and then the water-repellent hydrophobic film according to claim 2 is formed. After coating a low-temperature-curable multifunctional ceramic coating material containing a conductive silicon dioxide compound on the surface, the coating is dried at room temperature and / or heated at about 210 ° C. to obtain a coating thickness of about 100 μm. The method for forming a low-temperature-curable multifunctional ceramic coating film according to claim 1 or 2, wherein: