KR20110050851A - Eco-friendly inorganic adhesive composition and its manufacturing method - Google Patents

Abstract

The present invention relates to an environmentally friendly inorganic adhesive composition and a method for producing the same. This is an inorganic adhesive composition, which is a mixture of hydrochloric acid, citric acid and aluminum dihydrogen phosphate as a raw material mixture obtained by mixing and grinding a subsidiary material consisting of zinc oxide, aluminum hydroxide, diatomaceous earth, activated kaolin, titanium dioxide, and magnesia to liquid sodium silicate as a main raw material. An additive made of a stirred aqueous solution is added and mixed. The raw material mixture is 30-50 wt% of liquid sodium silicate, 15-30 wt% of zinc oxide, 10-20 wt% of aluminum hydroxide, based on 100 wt% of the raw material mixture, 10-20% by weight of diatomaceous earth, 5-10% by weight of activated kaolin, 2-5% by weight of titanium dioxide, and 2-7% by weight of magnesia, followed by milling and grinding; The additive is stirred by mixing 5 to 10% by weight aqueous solution of hydrochloric acid, 10 to 30% by weight aqueous solution of citric acid, and 10 to 30% by weight aqueous solution of aluminum dihydrogen phosphate at a weight ratio of 1 to 5: 1 to 2 to 1 to 5, respectively. Is done by; 5 to 25 parts by weight of the additive is added to 100 parts by weight of the raw material mixture, mixed and ground. Accordingly, the water resistance is strong and can be manufactured by a continuous production and / or a simple process to reduce the cost as well as to provide an environment-friendly inorganic adhesive composition and the like.

Description

Friendly Environment Inorganic Adhesive Composition and Manufacturing Method Thereof}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally relates to a building material or a multipurpose nonflammable inorganic adhesive composition, and more particularly, to a raw material mixture obtained by milling and mixing liquid sodium silicate with a raw material such as powdered sodium silicate, zinc oxide, aluminum hydroxide, activated kaolin, and the like. By mixing and mixing with the mixed solution of citric acid and the like, the water resistance is strong and can be manufactured by continuous production and / or a simple process, which can reduce costs and replace organic adhesives that are harmful to humans and the environment. A new environmentally friendly inorganic adhesive composition and a method for producing the same.

Generally, silicate materials such as sodium silicate and potassium silicate are well known as representative inorganic binders, and are widely used as heat-resistant, chemical-resistant, and waterproof coating materials because of their high thermal stability and environmental friendliness, unlike organic adhesives obtained from petrochemicals. In particular, liquid sodium silicate has a high viscosity and high adhesive strength as the amount of water decreases, and thus, when applied to the surface to be bonded, the liquid sodium silicate has a glass-like smooth coating and excellent effect as an adhesive.

However, the coated and dried silicate is easily re-dissolved in water or water in the air, so its use is very limited unless it is insoluble. The easiest way to insolubilize the liquid sodium silicate is to slowly heat-treat at a high temperature of 500 ° C. or more, but it is also limited to the use due to the stability of the adherend and the working environment. Therefore, attempts have been made to realize insolubilization by adding an appropriate additive to liquid sodium silicate.

In the insolubilization of liquid sodium silicate, not only the type of additive but also the amount of use should be carefully controlled. For example, in order to insolubilize silicate, there are many known methods of direct treatment with acid or polyvalent metal ions (eg Zn ⁺² , Cu ^+2, etc.). In this case, the reaction proceeds so fast that the monolayer ) Only insolubilized or too fast gelation due to the rapid volume reduction of the silicate has a problem of cracking on the surface of the adhesive surface.

In order to make an adhesive that does not generate cracks or micropores at room temperature and does not dissolve well in water, it is important to find a raw material that reacts slowly and insoluble, and to make each raw material have insoluble as well as high adhesive strength by complementary action. The establishment of processes is also an important factor. On the other hand, there is an example of the development of an insoluble binder using a conventional liquid sodium silicate, there are examples of Republic of Korea Patent Registration No. 10-0556902, Patent Publication No. 10-2005-0056186 and Patent Publication No. 10-2005-0056185. In these prior art to create a high concentration of sulfuric acid, hydrochloric acid, phosphoric acid, silicate by gradually reacting the acid in the liquid sodium silicate zero binder and grouting 0.05 to calcium carbonate of about 1.0% by weight of a very small amount (CaCO _3), calcium nitrate (Ca (NO _{3 2} ), magnesium chloride (MgCl ₂ ), magnesium sulfate (MgSO ₄ ), and alkaline earth metals such as calcium hydroxide (Ca (OH) ₂ ) are added to prepare an insoluble binder.

However, in this conventional manufacturing method, since a high concentration of acid is used, even when a small amount of high concentration of acid is added to the liquid sodium silicate in a rotating reactor, the liquid sodium silicate in contact with the acid is rapidly gelled, which makes stirring very difficult. Even after stirring for 3 hours or more, the gelled silicic acid and sodium salt were not easily dissolved, and it was confirmed that they remained in the form of fine lumps. These fine agglomerates can cause a decrease in bond strength and a factor of insolubility, which makes the process management very difficult.

In the process of adding 0.05 to 1.0% by weight of alkaline earth metal to the primary product produced in the above process, a delicate mixing process of adding a small amount of additives and mixing uniformly is added, thereby resulting in inhomogeneity in the adhesive production process of the entire manufacturing process. It is also possible to cause a whitening phenomenon by reacting with moisture in the air over time. Most importantly, the insolubility test and the mechanical strength test are not suitable for the use of adhesives at room temperature in that they are tested by mixing binder, perlite, zeolite, carbon, etc., and heat-treating them at a temperature above 100 ℃. do.

In addition, the Republic of Korea Patent Publication Nos. 10-2006-0043360 and 10-2006-0092783 also require properties such as water resistance, adhesion, sound absorption, heat insulation, impact absorption, ultra-light weight, low cost, completely nonflammable, completely pollution-free The present invention relates to foam moldings for construction and industrial use in various industries, and to the manufacture of inorganic binders used in manufacturing foam moldings. In detail, as in the aforementioned Korean Patent Nos. 10-0556902, 10-2005-0056186, and 10-2005-0056185 mentioned above, in addition to hydrochloric acid, sulfuric acid, and phosphoric acid, potassium chloride and quicklime are added to liquid sodium silicate. Acids such as ammonium chloride, alcohol, etc. (Potassium chloride, quicklime, ammonium chloride are basic substances, so there was error.) Aluminum chloride, sodium aluminate, arsenic chloride, sodium arsenite, arsenic chloride, chromium (III) chloride, sodium chromate Incompletely gelled silicate by administering amphoteric oxides or amphoteric hydroxides, including zinc hydroxide, arsenic hydroxide, tin hydroxide, tin hydroxide, chromium (III) hydroxide, zinc acid, arsenic acid, orthotinic acid, achromic acid, and the like, and gelling sodium silicate incompletely. The method of making sodium is described.

In this technique, it is possible to increase the bond strength by excessively accelerating incomplete gelation by increasing the amount of acid, and decrease the bond strength by reducing the amount of acid. However, there is no description of how to cope with the excessive increase in viscosity that occurs when the incomplete gelation is excessively promoted. In addition, as mentioned in the Republic of Korea Patent Nos. 10-0556902, 10-2005-0056186 and 10-2005-0056185 mentioned above, there is no mention of the degree of insolubility in curing at room temperature, It is difficult to grasp the physical properties of the binder because there is no mention of the mechanical strength of the foamed molded article formed by rapid drying at a high temperature of 150 ℃ ~ 600 ℃ using the prepared binder.

Liquid sodium silicate is a transparent or semi-transparent solution showing viscous alkalinity. The molar ratio of liquid sodium silicate in Korea Industrial Standard (KS M 1415) is 1: 2.064 ~ 4.300 for Na ₂ O and SiO ₂ . Have Such liquid sodium silicate has various inherent adhesive strengths, and is used in various ways such as cement additives to improve adhesives and soft ground, and it is widely used because of its simple manufacturing process, simple equipment, and low production cost than other adhesives. It is becoming. In particular, unlike organic adhesives in the manufacturing process, formaldehyde emitted from most organic adhesives does not emit liquid sodium silicate at all, and thus has been spotlighted in terms of environmental friendliness.

However, when the liquid sodium silicate is used as an adhesive, the sodium ions contained in the sodium silicate easily react with water or water in the air to form salts such as sodium hydroxide. The problem is that the strength is lowered and it can no longer serve as an adhesive. Because of these problems, some are adding raw materials such as carbon, zeolite, ocher, illite, etc. to liquid sodium silicate, but it is still difficult to prevent the elution of essential sodium salts as well as the price or deterioration of adhesive strength compared to conventional organic adhesives. This is the reality.

The present invention has been invented to improve the inorganic adhesive technique using the conventional liquid sodium silicate described above and to provide various additional advantages. The present invention is added to the liquid sodium silicate, a certain ratio of additives such as powdered sodium silicate, zinc oxide, aluminum hydroxide, diatomaceous earth, activated kaolin, titanium dioxide, magnesia, or aluminum phosphate added instead of aluminum dihydrogen phosphate added to the aqueous solution and additives By adding an appropriate amount of an aqueous solution of hydrochloric acid, citric acid, and aluminum dihydrogen phosphate solution at a constant ratio, the insolubilization reaction of the secondary raw material and the liquid sodium silicate and the crystallization of sodium inorganic acid due to the additives are released. It is possible to manufacture inorganic adhesive with no water resistance, and simple device and continuous production is possible when using circular attrition mill, so the process is simple and the overall manufacturing cost can be reduced, and organic compound harmful to human body and environment Do not use solvents made of environmentally friendly Its purpose is to provide a chemically versatile non-flammable inorganic adhesive.

The above object is achieved by an environmentally friendly inorganic adhesive composition and a method for producing the same, which are provided according to the present invention.

Inorganic adhesive composition provided according to an aspect of the present invention, in the raw material mixture obtained by mixing and grinding a secondary raw material consisting of zinc oxide, aluminum hydroxide, diatomaceous earth, activated kaolin, titanium dioxide, and magnesia to liquid sodium silicate as a main raw material, A mixture of hydrochloric acid, citric acid, and aluminum dihydrogen phosphate is added and mixed with an additive solution. The raw material mixture is 30-50 wt% of liquid sodium silicate and 15-30 wt% with respect to 100 wt% of the raw material mixture. %, 10-20% by weight of aluminum hydroxide, 10-20% by weight of diatomaceous earth, 5-10% by weight of activated kaolin, 2-5% by weight of titanium dioxide, 2-7% by weight of magnesia, followed by milling and grinding; The additive is stirred by mixing 5 to 10% by weight aqueous solution of hydrochloric acid, 10 to 30% by weight aqueous solution of citric acid, and 10 to 30% by weight aqueous solution of aluminum dihydrogen phosphate at a weight ratio of 1 to 5: 1 to 2 to 1 to 5, respectively. Is done by; 5 to 25 parts by weight of the additive is added to 100 parts by weight of the raw material mixture, mixed and ground.

Inorganic adhesive composition provided according to another aspect of the present invention, liquid sodium silicate, a mixture of zinc oxide, aluminum hydroxide, diatomaceous earth, activated kaolin, a secondary material consisting of titanium dioxide, magnesia, aluminum phosphate, hydrochloric acid, citric acid, It is mixed by adding the additive which becomes the aqueous solution which mixed and stirred aluminum dihydrogen phosphate; The raw material mixture is 30 to 50% by weight of liquid sodium silicate, 15 to 30% by weight of zinc oxide, 10 to 20% by weight of aluminum hydroxide, 10 to 20% by weight of diatomaceous earth, and 5 to 10% by weight of activated kaolin based on 100% by weight of the raw material mixture. Milling, pulverization and mixing consisting of 2-7 wt% of%, 2-5 wt% of titanium dioxide, 2-7 wt% of magnesia, and aluminum phosphate; The additive is made by mixing 5 to 10% by weight aqueous solution of hydrochloric acid, 10 to 30% by weight aqueous solution of citric acid in a weight ratio of 1 to 5: 1 to 2, respectively; 10 to 25 parts by weight of the additive is added to 100 parts by weight of the raw material mixture, mixed and pulverized.

In one embodiment, the liquid sodium silicate has a molar ratio of SiO ₂ / Na ₂ O of 3.0 to 3.3, specific gravity of 1.35 to 1.45, and total solids of 35 to 45%.

In another embodiment, to adjust the viscosity, 3 to 8% by weight of powdered sodium silicate having a SiO ₂ / Na ₂ O molar ratio of 3.0 to 3.3 is added to 100% by weight of the raw material mixture.

In still another embodiment, the zinc oxide has a purity of at least 99.5%, an average particle diameter of 0.5-0.8 μm, the aluminum hydroxide has a purity of 99.5% or more, an average particle diameter of 1-10 μm, the diatomaceous earth has an average particle diameter of 20-70 μm, The active kaolin has an average particle diameter of 20 to 70 µm, the titanium dioxide has an average particle diameter of 10 µm or less, and the magnesia has an average particle diameter of 10 to 30 µm.

Method for producing an inorganic adhesive composition provided according to another aspect of the present invention, as an additive manufacturing step, 5 to 10% by weight aqueous solution of hydrochloric acid, 10 to 39% by weight aqueous solution of citric acid, and 10 to 30% by weight aqueous solution of aluminum dihydrogen phosphate To prepare, and mixing each aqueous solution in a weight ratio of 1 to 5: 1 to 2: 1 to 5 by using a stirrer (11, 12); As a raw material mixture preparation step, 30 to 50% by weight of liquid sodium silicate, 15 to 30% by weight of zinc oxide, 10 to 20% by weight of aluminum hydroxide, 10 to 20% by weight of diatomaceous earth, 5 to 10% by weight of active kaolin, based on the total weight of the raw material mixture Adding 2 to 5 wt% of titanium dioxide and 2 to 7 wt% of magnesia to uniformly grind and mix them (13 and 14); Step 15 of making the final inorganic adhesive composition by adding and mixing the prepared aqueous solution additive to the prepared raw material mixture.

According to another aspect of the present invention, there is provided a method of preparing an inorganic adhesive composition, as an additive manufacturing step, preparing a 5-10 wt% aqueous solution of hydrochloric acid and a 10-39 wt% aqueous solution of citric acid, using a stirrer to prepare each aqueous solution. Mixing 11 to 12 in a weight ratio of 1 to 2; As a raw material mixture preparation step, 30 to 50% by weight of liquid sodium silicate, 15 to 30% by weight of zinc oxide, 10 to 20% by weight of aluminum hydroxide, 10 to 20% by weight of diatomaceous earth, 5 to 10% by weight of active kaolin, based on the total weight of the raw material mixture (13, 14) grinding and mixing uniformly by adding 2 to 5 wt% of titanium dioxide, 2 to 7 wt% of magnesia, and 2 to 7 wt% of aluminum phosphate; Step 15 of making the final inorganic adhesive composition by adding and mixing the prepared aqueous solution additive to the prepared raw material mixture.

In one embodiment, the apparatus for mixing and pulverizing the raw materials in the raw material mixture manufacturing step 15 is preferably a ball mill or a circular attrition mill.

In another embodiment, prior to mixing the zinc oxide to magnesia in the liquid sodium silicate in the raw material mixture manufacturing step 15, it may further comprise the step of dissolving by adding powdered sodium silicate to the liquid sodium silicate.

In another embodiment, the step 15 of making the final inorganic adhesive composition by adding and mixing the prepared aqueous solution additive to the prepared raw material mixture is prepared in a device in which the prepared raw material mixture is ground and mixed. It is preferable to proceed by adding the aqueous solution additive.

In still another embodiment, the method may further include adding an inorganic pigment to add color to the prepared inorganic adhesive.

According to the present invention having the above-described configuration, it is possible to manufacture a strong water-resistant inorganic adhesive without releasing to the water or water in the air, the device is simple and continuous production is possible when using a circular attrition mill process This simplicity can reduce the overall manufacturing cost, and can provide an environmentally friendly and versatile non-flammable inorganic adhesive by not using a solvent composed of organic compounds harmful to humans and the environment.

In addition, according to the inorganic adhesive composition according to the present invention and a method for manufacturing the same, the curing time is shortened even at room temperature, the bonding strength when completely cured, compared to other products, easy to work during construction, and harmful substances such as formaldehyde It is not generated, it has antibacterial function due to photocatalytic action on the coated surface, it does not generate mold, has far infrared radiation effect, does not generate toxic gas due to burning of adhesive in fire, and is manufactured by simple work process using relatively easy raw materials It can increase the price competitiveness by reducing the manufacturing cost, and by adding a simple process, it is possible to produce products such as anti-corrosive coating, eco-friendly antibacterial mortar, eco-friendly inorganic non-flammable paint, adhesive for wood.

The most important of these is the ever-increasing preference for eco-friendly products, in line with increasingly stringent indoor air standards. Therefore, the demand for eco-friendly products such as the present invention will continue to increase and it will be that the prepared a bridgehead to cope with this.

Hereinafter, with reference to the accompanying drawings illustrating the present invention with a specific example as follows.

1 is a schematic flowchart showing the steps of a method for producing an environmentally friendly inorganic adhesive composition according to an embodiment of the present invention, Figure 2 is a photograph showing the product state of the environmentally friendly inorganic adhesive composition according to an embodiment of the present invention, 3 is a photograph showing a state of applying the environmentally friendly inorganic adhesive composition of Figure 2 on a wooden specimen.

Eco-friendly inorganic adhesive composition provided by the present invention, liquid sodium silicate, powdered sodium silicate, zinc oxide, aluminum hydroxide, diatomaceous earth, activated kaolin, titanium dioxide, magnesia, aluminum phosphate which is added instead of aluminum dihydrogen phosphate added to the aqueous solution It consists of a raw material mixture consisting of and a mixed aqueous solution additive of hydrochloric acid, citric acid, aluminum dihydrogen phosphate.

Preferably, the raw material mixture is 30-50 wt% of liquid sodium silicate, 3-8 wt% of powdered sodium silicate, 15-30 wt% of zinc oxide, 10-20 wt% of aluminum hydroxide, 10-20 wt% of diatomaceous earth, activated kaolin 5 to 10% by weight, 2 to 5% by weight of titanium dioxide, 2 to 7% by weight of magnesia is ground and mixed using a ball mill or an attraction mill (steps 13 and 14 of Figure 1).

Aqueous solution additives were prepared by using a stirrer in a weight ratio of 5 to 10% by weight aqueous solution of hydrochloric acid, 10 to 30% by weight aqueous solution of citric acid, and 10 to 30% by weight aqueous solution of aluminum dihydrogen phosphate in a ratio of 1 to 5: 1 to 2: 1 to 5, respectively. It is prepared by mixing (steps 11 and 12 of FIG. 1).

The mixed inorganic solution additive may be added to the above raw material mixture by adding 5-25 parts by weight to 100 parts by weight of the raw material mixture, and then mixing the resultant inorganic adhesive composition by using a ball mill or attrition mill. (15 steps of FIG. 1).

In a preferred embodiment, the liquid sodium silicate has a molar ratio of SiO ₂ / Na ₂ O of about 3.0 to 3.3, specific gravity of 1.35 to 1.45 and total solids of 35 to 45%. On the other hand, the powdered sodium silicate may have the same molar ratio as for example 3.1 of liquid sodium silicate. Zinc oxide has a purity of 99.5% or more and an average particle diameter of 0.5 to 0.8 µm, aluminum hydroxide has a purity of 99.5% or more and an average particle diameter of 1 to 10 µm, diatomaceous earth has an average particle diameter of 20 to 70 µm, and activated kaolin has an average particle diameter of 20 to 70 µm. It is preferable that it is micrometer, titanium dioxide is 10 micrometers or less in average particle diameter, and magnesia is 10-30 micrometers in average particle diameter.

In the method for preparing an inorganic adhesive composition according to the present invention, as shown in FIG. 1, a ball mill or a metered dose of powdered sodium silicate, zinc oxide, aluminum hydroxide, diatomaceous earth, activated kaolin, titanium dioxide, and magnesia is added to liquid sodium silicate. Steps 13 and 14 of wet mixing and grinding using an attrition mill to prepare a raw material mixture, and an aqueous solution of hydrochloric acid, citric acid and aluminum dihydrogen phosphate are prepared using a stirrer using general water as a solvent. Mixing the aqueous solution at a constant ratio to form an aqueous solution additive (11, 12), and the aqueous and additive additive in a predetermined quantitative ratio to the mixed and pulverized raw material mixture, followed by re-mixing and grinding (15) Discharging the environmentally friendly nonflammable inorganic adhesive 16 may be performed.

Although not shown hereafter, as a subsequent process that may be added before the inspection (17) and packaging / shipping (18) steps, water or liquid sodium silicate or zinc oxide, aluminum hydroxide, diatomaceous earth, activated kaolin are added to the prepared inorganic adhesive. By using a ball mill or attrition mill or a high speed stirrer to adjust the viscosity or to add a variety of inorganic pigments may be added. According to this subsequent process, the inorganic adhesive composition provided in the present invention can finally be made as an anti-corrosion coating, an environmentally friendly antibacterial mortar, an environmentally friendly inorganic non-combustible paint product. The manufactured product can then be inspected and packed / unloaded according to the specified specifications.

In this manufacturing process, the step (15) of making the final inorganic adhesive composition by adding and mixing the aqueous solution additive to the raw material mixture is an aqueous solution prepared above in a ball mill or a circulation attrition mill which is a device in which the prepared raw material mixture is mixed and ground. It can proceed by adding an additive. In this case, since the apparatus used in the process 14 for crushing and mixing the raw material mixture is reused in the crushing and mixing process 15 for producing the final composition, the manufacturing process can be simplified and the manufacturing cost can be reduced. In this case, it is preferable to mix a raw material mixture, ie, a mixed slurry, for 3 to 4 hours in a ball mill using a ball mill or a circulation attrition mill, and to mix within an hour in an attrition mill. If the final inorganic adhesive composition is prepared by using a device other than the raw material mixture, that is, the mixed slurry, that is, when mixing the mixed aqueous solution to the mixed slurry in a separate mixer, the mixing time is 2 It is preferable not to exceed 30 minutes in time and an attention mill.

As described above, the present invention relates to a composition of an environmentally friendly non-flammable inorganic adhesive that can be used for building materials and other multipurposes, and to a method of manufacturing the same. More specifically, the adhesive bond itself quickly reaches the maximum bond strength even at room temperature, and the temporary curing time after the work is short, and the remaining residue can be removed only by washing the water after the work, and thus the work is easy, and the durability and chemical resistance are excellent. The present invention relates to a composition and a method for preparing an environmentally friendly non-combustible inorganic adhesive having no anti- formaldehyde, antibacterial and far-infrared radiation by photocatalytic action, and having a relatively competitive price compared to conventional organic adhesives. In order to have such a function, the above-mentioned subsidiary materials and additives were required, and there were changes in curing time, bonding strength, insolubilization state over time, depending on the input amount of each sub-material and the mixing ratio and raw material input amount for preparing the added aqueous solution. The results are shown in Table 1, Table 2, Table 3, Table 4, Table 5, and Table 6.

In the present invention, raw materials such as zinc oxide, aluminum hydroxide, diatomaceous earth, activated kaolin, titanium dioxide, and magnesia are added to the liquid sodium silicate, and the zinc oxide is combined with water and hydroxide ions in the liquid sodium silicate to form Zn (OH) ₂ as follows. ^It is known to form ^-4 .

Scheme 1

^{_{ZnO + H 2 O + OH -}} → Zn (OH) 2 -4

In this reaction, the concentration of hydroxyl ions at the surface decreases, and the liquid sodium silicate in this portion forms a polymerization reaction of the following Scheme 2 to form an insoluble silica gel.

Scheme 2

The zinc ions on the surface of the particles also form zinc silicate (Zn ₂ SiO ₄ ), which is also insoluble in water, which also promotes insolubilization of sodium silicate. However, the above reaction proceeds to a certain degree even at room temperature, but the progress of the reaction is very slow, which is an important disadvantage of the role as an adhesive. Therefore, in order to speed up the reaction, a heat treatment process is performed for separate drying, which also has many restrictions on the working environment as an adhesive. In addition, when the heat treatment process is a problem that the moisture contained in the adhesive is rapidly evaporated to cause a fine crack on the surface. Therefore, activated kaolin, diatomaceous earth, and magnesia are also acidic in water, and when they are mixed with liquid sodium silicate, they have been found to be insoluble due to the above polymerization reaction, and activated kaolin hardens faster than zinc oxide. In addition, diatomaceous earth and magnesia contribute to hardening and act as a buffer due to the low specific gravity of raw materials, which prevents cracks on the surface and prevents various problems caused by excessive shrinkage during hardening. In addition, in the present invention, aluminum hydroxide reacts with liquid sodium silicate together with aluminum dihydrogen phosphate in the aqueous solution to produce insoluble aluminum silicate to promote insolubilization reaction, and uniform insolubilization reaction occurs in the entire insoluble adhesive to bond strength. Can be increased significantly. The above results are shown in Table 1. In addition, titanium oxide is a building material, which enhances the whiteness of the adhesive, produces a photocatalytic effect, enhances antibacterial effect, and has excellent acid and alkali resistance, thereby enhancing chemical resistance. In addition, the addition of hydrochloric acid, citric acid and aluminum dihydrogen phosphate solution delays the rapid crystallization of sodium salt than when hydrochloric acid alone is added, which facilitates the manufacturing process of the adhesive and further improves the quality of the adhesive by enhancing the insolubility and adhesive strength. Play a role. The results are shown in Table 2. In detail, the hydrochloric acid forms silicon dioxide, water, and sodium salts through the liquid sodium silicate and the following reaction scheme 3, and the sodium salt is stable to moisture because it is present as crystals.

Scheme 3

Na ₂ OSiO ₂ + 2HCl → SiO ₂ + 2NaCl + H ₂ O

However, the addition of excessive hydrochloric acid only accelerates the insoluble gelation due to the rapid reaction with liquid sodium silicate, there are many problems in the manufacturing process as well as the adhesive strength is reduced, there are many restrictions in obtaining an adhesive of good properties. However, if the amount of hydrochloric acid is not sufficient, the partial reaction with liquid sodium silicate causes sodium ions to remain, resulting in a problem of poor stability to moisture.

Therefore, in the present invention, dilute hydrochloric acid with 5 to 10% by weight aqueous solution, prepare a mixed solution mixed with a 10 to 30% by weight aqueous solution of citric acid and 10 to 30% by weight aqueous solution of aluminum dihydrogen phosphate in a constant ratio to rapidly conduct gelation. The process was controlled. The addition of aqueous hydrochloric acid, citric acid, and aluminum dihydrogen phosphate solution in the mixture already stabilized in water by the addition of subsidiary materials such as zinc oxide, aluminum hydroxide, diatomaceous earth, activated kaolin, enhances the water insolubility up to the inside of the adhesive, It can be said that it is important to remove the pores in the adhesive, and to see the effect of improving the bonding strength more.

In particular, aluminum dihydrogen phosphate, together with aluminum hydroxide in the mixed slurry, produces partially incomplete aluminum silicate to enhance insolubility and bonding strength. The reaction between the additive aluminum hydroxide and aluminum dihydrogen phosphate with liquid sodium silicate is shown in Scheme 4 below.

Scheme 4

9Na ₂ OSiO ₂ + 2Al (H ₂ PO ₄ ) ₃ → Al ₂ O ₃ 9SiO ₂ + 6Na ₃ PO ₄ + 6H ₂ O

3Na ₂ OSiO ₂ + 2Al (OH) ₃ → Al ₂ O ₃ 3SiO ₂ + 6NaOH

In addition, aluminum dihydrogen phosphate was more soluble in water and more efficient than aluminum phosphate in terms of bonding strength and shortening of complete curing time. However, if necessary, aluminum phosphate was used instead of aluminum dihydrogen phosphate in the slurry mixing process. It is okay to do it.

As described above, the present invention adopts an additive and an aqueous solution through various experiments to obtain quality competitiveness such as bonding strength, curing time, and stability of the adhesive. It is resistant to moisture and water, and can be manufactured at low cost due to its simple manufacturing equipment and processes, and can reduce manufacturing costs. The final results of the present invention, which can be usefully used as binders and coating agents for various purposes, are shown in Table 1, Table 2, Table 3, Table 4, Table 5, and Table 6, and the photographs of the final products are shown in FIG. It was.

The present invention relates to an environmentally friendly non-flammable inorganic adhesive that can be used as a building material and versatile, and has superiority in terms of functionality and economics compared to existing products, and particularly has a high curing rate even at room temperature and is not eluted by moisture. It has the advantage that it can be improved and its use can be widened.

The particle size of each raw material required to produce a multipurpose, eco-friendly non-flammable inorganic adhesive produced through a series of manufacturing processes as mentioned above is preferably determined according to the specific gravity of each raw material as much as possible, and this is a ball mill or a The treatment mill is used to maximize the effect of dispersion during the grinding and mixing process to help maximize the reactivity with the liquid sodium silicate and shorten the grinding and mixing time.

In addition, since the amount of each raw material may be a decisive factor for insolubility and bonding strength by water, the input amount was determined as a condition that yields the most optimal result through many experiments and analysis of experimental results.

Bonding strength was measured according to the tensile strength measurement criteria of "KSF 4716 Cement Based Coating Material" and "KSF3218 Vinyl Floor Adhesive", which are the building material test requirements. After curing time, 3 mm / min. Pulled up and down at a speed of measured. Each raw material addition amount was measured by varying the bonding strength by increasing only the addition amount of the raw material to be tested while the input amount of the raw materials other than the added raw material was fixed.

In detail, the input of the powdered sodium silicate, diatomaceous earth, titanium dioxide, and magnesia was fixed, and only the raw materials to be tested among zinc oxide, aluminum hydroxide, and activated kaolin were measured while changing the addition amount. The total weight ratio was adjusted to 100% by weight by reducing the amount of liquid sodium silicate as the amount of the raw material to be tested increases in the total weight ratio. The measurement results are shown in Table 1.

TABLE 1

TABLE 2

In addition, the change in curing time according to the amount of activated kaolin was made under the same conditions as the measurement of the bonding strength, and the most suitable conditions were determined by measuring the bonding strength of each specimen over 4 hours, 12 hours, 24 hours and 48 hours. . The change in curing time according to the amount of activated kaolin and mixed water solution is shown in Tables 3 and 4.

[Table 3]

[Table 4]

In addition, the test for changing the elution amount of sodium salt according to the amount of each raw material was applied to each wood specimen to measure the total weight of each 5.000g adhesive, and cured at room temperature for 48 hours, and then accurately measured 100.000g of water and placed in a beaker. 48 hours after the specimen was in contact with the coated surface and the water was taken out and dried for 8 hours in a forced circulation dryer at 60 ~ 70 ℃ and the weight change of the specimen was measured. The elution amount of sodium salt according to the amount of each raw material is shown in Tables 5 and 6. In addition, an example of applying the adhesive to the wood specimens is shown in FIG.

TABLE 5

TABLE 6

In conclusion, as the amount of zinc oxide increased, the elution of bonding strength and sodium salt decreased drastically, and the addition of 10% by weight of aluminum hydroxide increased the bonding strength, but the amount of sodium elution increased. As the added amount of activated kaolin increased, hardening time, insolubility, and bond strength were increased. In particular, the strength of the adhesive can be said to be the result of the addition of activated kaolin to improve the insoluble not only on the surface of the adhesive but also to the inside and promotes curing. Therefore, it can be seen that activated kaolin plays an important role in improving the physical properties of the overall adhesive. These results contributed greatly to the development of adhesives having the desired properties at the best combination ratio, and the combination ratio is shown in Table 7. However, the present invention is not limited to the range of the combination ratio in Table 7 and the product development should be made through continuous experiments and development within the dosage range of the mixture specified above. In addition, this invention does not mention the characteristic of the adhesive obtained by applying separate heat. Although the adhesive of the present invention brings about 50 to 80% of the adhesive strength and a shortening of the curing time when working at room temperature to promote curing, but the purpose of the present invention is to provide an adhesive when working at room temperature. It is said that it is different from other similar products.

TABLE 7

Although the present invention has been described through specific embodiments, various modifications are possible to those skilled in the art by referring to and combining various features described herein. Therefore, it should be pointed out that the scope of the present invention should not be limited to the described embodiments, but should be interpreted by the appended claims.

As described above, the eco-friendly inorganic adhesive composition and the manufacturing method thereof according to the present invention can be widely used in the field of building materials and / or multi-purpose eco-friendly non-flammable adhesives.

1 is a schematic flow chart showing the steps of a method for producing an environmentally friendly inorganic adhesive composition according to an embodiment of the present invention.

Figure 2 is a photograph showing the product state of the eco-friendly inorganic adhesive composition according to an embodiment of the present invention.

Figure 3 is a photograph showing a state of applying the environmentally friendly inorganic adhesive composition of Figure 2 on a wooden specimen.

Claims (11)

As an environmentally friendly inorganic adhesive composition, a mixture of hydrochloric acid, citric acid and aluminum dihydrogen phosphate is mixed with a raw material mixture obtained by mixing and grinding a subsidiary material consisting of zinc oxide, aluminum hydroxide, diatomaceous earth, activated kaolin, titanium dioxide, and magnesia, with liquid sodium silicate as a main raw material. It is mixed by adding an additive of a stirred aqueous solution, The raw material mixture is 30 to 50% by weight of liquid sodium silicate, 15 to 30% by weight of zinc oxide, 10 to 20% by weight of aluminum hydroxide, 10 to 20% by weight of diatomaceous earth, and 5 to 10% by weight of activated kaolin based on 100% by weight of the raw material mixture. %, 2 to 5% by weight of titanium dioxide, 2 to 7% by weight of magnesia are mixed and milled and ground; The additive is stirred by mixing 5 to 10% by weight aqueous solution of hydrochloric acid, 10 to 30% by weight aqueous solution of citric acid, and 10 to 30% by weight aqueous solution of aluminum dihydrogen phosphate at a weight ratio of 1 to 5: 1 to 2 to 1 to 5, respectively. Is done by; Eco-friendly inorganic adhesive composition, characterized in that the composition by mixing and grinding by adding 5 to 25 parts by weight of the additive relative to 100 parts by weight of the raw material mixture. Eco-friendly inorganic adhesive composition comprising a mixture of hydrochloric acid, citric acid and aluminum dihydrogen phosphate mixed with liquid sodium silicate and a mixture of zinc oxide, aluminum hydroxide, diatomaceous earth, activated kaolin, titanium dioxide, magnesia and aluminum phosphate It is mixed by adding the additive in the aqueous solution; The raw material mixture is 30 to 50% by weight of liquid sodium silicate, 15 to 30% by weight of zinc oxide, 10 to 20% by weight of aluminum hydroxide, 10 to 20% by weight of diatomaceous earth, and 5 to 10% by weight of activated kaolin based on 100% by weight of the raw material mixture. Milling, pulverization and mixing consisting of 2-7 wt% of%, 2-5 wt% of titanium dioxide, 2-7 wt% of magnesia, and aluminum phosphate; The additive is made by mixing 5 to 10% by weight aqueous solution of hydrochloric acid, 10 to 30% by weight aqueous solution of citric acid in a weight ratio of 1 to 5: 1 to 2, respectively; Eco-friendly inorganic adhesive composition, characterized in that the composition by mixing and grinding by adding 10 to 25 parts by weight of the additive relative to 100 parts by weight of the raw material mixture. The method according to claim 1 or 2, The liquid sodium silicate has a molar ratio of SiO ₂ / Na ₂ O of 3.0 to 3.3, specific gravity of 1.35 to 1.45, and total solids content of 35 to 45%. The method according to claim 1 or 2, In order to adjust the viscosity, 3 to 8% by weight of powdered sodium silicate having a SiO ₂ / Na ₂ O molar ratio of 3.0 to 3.3 is added to 100% by weight of the raw material mixture. Adhesive composition. The method according to claim 1 or 2, The zinc oxide has a purity of 99.5% or more, an average particle diameter of 0.5-0.8 μm, the aluminum hydroxide has a purity of 99.5% or more, an average particle diameter of 1-10 μm, the diatomaceous earth has an average particle diameter of 20-70 μm, and the active kaolin has an average particle diameter of 20- 70 μm, the titanium dioxide has an average particle diameter of 10 μm or less, and the magnesia has an average particle diameter of 10 to 30 μm, eco-friendly inorganic adhesive composition. As a method for producing an environmentally friendly inorganic adhesive composition, As an additive manufacturing step, 5 to 10% by weight aqueous solution of hydrochloric acid, 10 to 39% by weight aqueous solution of citric acid, and 10 to 30% by weight aqueous solution of aluminum dihydrogen phosphate were prepared, and each aqueous solution was prepared by using a stirrer 1 to 5: 1 to 1 2: mixing at a weight ratio of 1 to 5 (11, 12), As a raw material mixture preparation step, 30 to 50% by weight of liquid sodium silicate, 15 to 30% by weight of zinc oxide, 10 to 20% by weight of aluminum hydroxide, 10 to 20% by weight of diatomaceous earth, 5 to 10% by weight of active kaolin, based on the total weight of the raw material mixture , 2 to 5% by weight of titanium dioxide, 2 to 7% by weight of magnesia to uniformly grind and mix (13, 14), Step 15 of making the final inorganic adhesive composition by adding and mixing the prepared aqueous solution additive to the prepared raw material mixture A method for producing an environmentally friendly inorganic adhesive composition, comprising: As a method for producing an environmentally friendly inorganic adhesive composition, As an additive manufacturing step, 5 to 10% by weight aqueous solution of hydrochloric acid and 10 to 39% by weight aqueous solution of citric acid are prepared, and mixing each aqueous solution in a weight ratio of 1 to 5: 1 to 2 using a stirrer (11, 12 )Wow, As a raw material mixture preparation step, 30 to 50% by weight of liquid sodium silicate, 15 to 30% by weight of zinc oxide, 10 to 20% by weight of aluminum hydroxide, 10 to 20% by weight of diatomaceous earth, 5 to 10% by weight of active kaolin, based on the total weight of the raw material mixture Adding and crushing and mixing uniformly by adding 2 to 5 wt% of titanium dioxide, 2 to 7 wt% of magnesia, and 2 to 7 wt% of aluminum phosphate (13, 14), Step 15 of making the final inorganic adhesive composition by adding and mixing the prepared aqueous solution additive to the prepared raw material mixture A method for producing an environmentally friendly inorganic adhesive composition, comprising: 8. The method according to claim 6 or 7, Apparatus for mixing and pulverizing the raw materials in the raw material mixture manufacturing step (15) is characterized in that the ball mill (ball mill) or cyclic Attrition mill (attrition mill), manufacturing method of environmentally friendly inorganic adhesive composition. 8. The method according to claim 6 or 7, Before mixing the zinc oxide to magnesia with the liquid sodium silicate in the raw material mixture manufacturing step 15, further comprising the step of dissolving by adding powdered sodium silicate to the liquid sodium silicate, eco-friendly inorganic adhesive composition Method of preparation. 8. The method according to claim 6 or 7, The step (15) of making the final inorganic adhesive composition by adding and mixing the prepared aqueous solution additive to the prepared raw material mixture is performed by adding the prepared aqueous solution additive to a device in which the prepared raw material mixture is ground and mixed. Method for producing an environmentally friendly inorganic adhesive composition, characterized in that. 8. The method according to claim 6 or 7, Further comprising the step of adding an inorganic pigment in order to add color to the prepared inorganic adhesive, eco-friendly inorganic adhesive composition manufacturing method.

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