KR101174372B1 - Preparation of waterproof inorganic silicate binder with fine structure of polymeric beads after curing and its manufacturing method - Google Patents

Abstract

The present invention relates to a method for producing a water-resistant silicate-based inorganic binder having a fine structure of the polymer beads at the time of curing, and adds liquid sodium silicate or potassium silicate with ion-exchanged water to a milling tank, and stirs the liquid lithium silicate. After adding and stirring, methyl methoxy silane, methyl triethoxy silane, triethoxy vinyl silane, diphenyldimethoxy silane, triethoxy silane, and the like are added to the reaction, and the reaction is performed at about 500 RPM until it is completely hydrolyzed. A hydrolysis step of stirring for at least 10 minutes to obtain a silicate solution; The agitator speed was increased to about 2000 RPM in the hydrolyzed silicate solution and slowly added alumina sol or silica sol having a colloidal particle size of 40 to 180 nm of alumina or silica until the viscosity was stabilized and the additive was completely hydrated. A viscosity adjusting step of stirring; In the viscosity control step, the viscosity is stabilized and the additive is hydrated, and under the operation of the dust control equipment, zinc oxide, tuff, diatomaceous earth, pozzolane of silica gel or metacaolin, and a particle size of 0.1 to 20 microns (μ) Phosphorus silicone rubber, fluorocarbon resin, polystyrene, polymer beads such as polyacrylic or polysulfone beads are added and stirred at 1000 rpm for 30 minutes or more to check 20 micron (μ) or less with a particle size meter, and then adjust the speed to 300 RPM to apply liquid wetting agent. A wetting step of injecting and stirring at least 10 minutes to obtain a water-resistant silicate-based inorganic binder (liquid silicate solution); To the water-resistant silicate inorganic binder (liquid silicate solution) obtained through the wetting step Hiding power reinforcing step of stirring and milling at 1000 RPM for at least 30 minutes by adding silica under the operation of the dust control equipment; A aging step of stirring the water-resistant silicate-based inorganic binder (liquid silicate solution) that has undergone the silver pen reinforcement step until the viscosity is stabilized, and then stabilizing the polymer beads and silica to react with the hydrated alumina sol or silica sol; In the commercialization step of completing the water-resistant silicate-based inorganic binder (liquid silicate solution) by adding the ion-exchange water to the water-soluble silicate-based inorganic binder (liquid silicate solution) after the aging step to adjust the viscosity to match the use, polymer beads 10 to 25% by weight, 20 to 45% by weight of liquid silicate or potassium silicate, 5 to 25% by weight of ion-exchanged water, 5 to 20% by weight of liquid lithium silicate, 1 to 5% by weight of reactive silane, 3 to 3% of zinc oxide Water-resistant silicate with fine structure of polymer beads upon curing composed of 7% by weight, 3-10% by weight of pozzolanic, 5-15% by weight of silica sol or alumina sol, 5.5-20% by weight of silica and 0.5-5% by weight of liquid wetting agent It is to obtain a type inorganic binder.

Description

Precipitation of waterproof inorganic silicate binder with fine structure of polymeric beads after curing and its manufacturing method}

The present invention relates to a water-resistant silicate-based inorganic binder having a fine structure of polymer beads upon curing, and a method of manufacturing the same.

In general, paint (painting, coating agent) is a flowable material is widely applied to the surface of the object to form a thin film layer, and dried and cured over time to protect the surface of the object and increase the aesthetics Have

Such paints are particularly applied to various structures such as buildings to enhance the appearance of the structures as well as to prevent damages such as corrosion and to improve durability.

Paints mainly used for the protection of structures such as buildings include oil paint, enamel paint, and water paint.

These paints not only protect the building, but also increase the aesthetics and improve the insulation and flame retardancy, while the durability and wear resistance are weak, causing the protective film to peel off or cracking, as well as far-infrared radiation, anion emission, The beneficial effects on the human body, such as humidity control, sterilization, antibacterial, detoxification, etc. are extremely insignificant.

As an example of hazardous substance emitting materials encountered in daily life, synthetic resin emulsion paints, volatile organic compounds (VOC) and heavy metals such as benzene, toluene, xylene and formaldehyde which are continuously released after coating the paint It has fatal hazards that can cause general paralysis, respiratory disease, headache, allergy and cancer.

As a countermeasure, the domestic paint industry replaces solvents with water instead of volatile organic compounds, increases the solid content ratio in paints, reduces relative solvent usage, or develops powder coatings without solvents. We are working to reduce pollution.

However, such a method can reduce environmental pollutants, but cannot eliminate them.

In the case of powder coating, a separate heat treatment process is required, so it is not applicable to concrete structures.

The paints used for construction are aimed at protecting and improving the aesthetics of the structure. In general, the paints used for building have no major problems in improving the aesthetics of the building structure. There are many problems.

In addition, in the case of synthetic resin emulsion paints, the remaining monomers remain in the polymerization of the emulsion, and thus general application of the environmental regulations is difficult.

Liquid silicates, such as sodium silicate, potassium silicate and lithium silicate, are non-toxic in aqueous form and are relatively inexpensive and incombustible compared to the raw materials of paints, adhesives, and specialty coatings made of petrochemical organic polymers. As a useful material, when it is formed as a thin film, it forms an inorganic bond or coating film which is dried and firmly and firmly, and is used as adhesives, detergents, and the like for various adhesives, binders and extenders for modifying textiles, fiber materials for ceilings and walls for construction and walls, etc. It is used in various fields such as coagulants, high heat-resistant coatings or electrode coatings for ceramic or powdery binders, coatings and finishes.

Inorganic binders using liquid silicates are economical, environmentally friendly, and inexpensive, and have economic advantages.However, when applied as a general paint that is cured and dried at room temperature, the bonding of liquid silicates or the resulting coating film is completely dried by drying for a long time. Until it is heated or dried at a very high temperature for a certain period of time, it is a fatal impossibility to apply it in a place requiring water resistance because it swells or penetrates by moisture, and thus it is still basic to silicate in Korea. The development of inorganic paints has been pointed out as a big reason for not being made smoothly, and it is simply not able to escape the limitation that is slightly applied for characteristic modification to some paints.

The present invention solves the weak water resistance defect of the liquid silicate binder by forming a protective film having a fine structure of hydrophobic polymer beads during the curing reaction by adding polymeric beads to solve the above problems. By increasing the flexibility of the coating film, it should be possible to produce a liquid silicate binder that has excellent waterproofing effect, fast drying speed and easy to paint.

 The polymer bead includes various states in which a polymerization reaction including crosslinking may be present in a reaction material or a reaction mixture in an organic phase in the form of independent particles in a liquid or solid state having a predetermined level or more.

Polymer beads are polymer particles having a degree of crosslinking, and can be broadly classified into non-porous beads having no pores and porous beads having pores, depending on the presence of pores.

Granular polymer beads, either by themselves or when undergoing further modification, are used as fillers to impart flexibility, hydrophobicity, low temperature stability, impact resistance, and flame retardancy to inorganic liquid silicate binders.

In order to solve the above problems, the present invention, liquid sodium silicate or potassium silicate is added to the milling tank with ion-exchanged water and sufficiently stirred, and then liquid lithium silicate is added and stirred, followed by methyltrimethoxysilane and methyl tree. A hydrolysis step of adding a reactive silane such as ethoxysilane, triethoxyvinylsilane, diphenyldimethoxysilane, triethoxysilane, and the like to stir at least about 10 minutes at 500 RPM until it is completely hydrolyzed to obtain a silicate solution;

The stirrer speed was increased to about 2000 RPM in the hydrolyzed silicate solution (binder) to slowly add a viscosity modifier made of alumina sol or silica sol having a colloidal particle size of 40 to 180 nm of alumina or silica to stabilize the viscosity and alumina sol. A viscosity adjusting step of stirring until the viscosity adjusting agent made of silica sol is completely hydrated; When the viscosity is stabilized in the viscosity control step and the viscosity control agent made of alumina sol or silica sol is hydrated, pozzolane of zinc oxide, tuff, diatomaceous earth, silicaca fume or metakaolin under the operation of the dust control equipment, and the particle size is 0.1 ~. 20 microns (μ) granular silicone rubber, fluorine resin, polystyrene, polyacryl or polysulfone beads, and polymer beads are added, and stirred at 1000 RPM for 30 minutes or more to determine 20 microns (μ) or less with a particle size meter, and then 300 RPM Wetting step to obtain a water-resistant silicate-based inorganic binder by stirring for 10 minutes or more by adding a liquid wetting agent after adjusting the speed; To the water-resistant silicate inorganic binder obtained through the wetting step Hiding power reinforcing step of stirring and milling at 1000 RPM for at least 30 minutes by adding silica under the operation of the dust control equipment; Aging step of stirring until the viscosity of the water-resistant silicate-based inorganic binder after the silver pen reinforcement step is stabilized to stabilize the polymer beads and silica to react with the hydrated alumina sol or silica sol; A commercialization step of completing the water-resistant silicate-based inorganic binder by adjusting the viscosity by adding ion-exchanged water to the intended use to the water-resistant silicate-based inorganic binder after the aging step, the polymer beads 10-25% by weight, liquid sodium silicate or 20 to 45% by weight of liquid potassium silicate, 5 to 25% by weight of ion-exchanged water, 5 to 20% by weight of liquid lithium silicate, 1 to 5% by weight of reactive silane, 3 to 7% by weight of zinc oxide, 3 to 10% by weight of pozzolan And a water-resistant silicate-based inorganic binder having a fine structure of polymer beads upon curing, which is composed of 5 to 15% by weight of silica sol or alumina sol, 5.5 to 20% by weight of silica and 0.5 to 5% by weight of liquid wetting agent.

As described above, the method of manufacturing a water-resistant silicate-based inorganic binder having a fine structure of the polymer beads during curing according to the present invention forms a protective film having a fine structure of the polymer beads during the curing reaction to solve the weak water-resistant defect of the liquid silicate binder. At the same time, by increasing the surface strength and flexibility of the coating, it has the advantage of producing a liquid silicate binder that has excellent waterproofing effect, fast drying speed and easy paintability.

In addition, by applying granular micron (μ) -scale polymer beads to a binder containing liquid sodium silicate, potassium liquid silicate and liquid lithium silicate as a main component, it is possible to prevent cracks and moisture generated during the curing process of a conventional building finishing material and over time. It is possible to improve the problems such as surface contamination caused by the use of water-based binders, and it does not generate volatile organic compounds that are harmful to the human body. Therefore, it provides an ecological and health-friendly living environment to the human body, and the coating layer formed after curing of the paint is excellent. Durability can be secured, and it is composed of an inorganic system, and has an advantage of excellent pollution prevention effect such as fine dust due to static electricity and easy construction.

1 is an exemplary embodiment of the present invention.
Figure 2 is an electron micrograph of the polymer bead of the present invention.
Figure 3 is an electron micrograph after curing of the water-resistant silicate-based inorganic binder of the present invention polymer beads.

To illustrate a specific method for the practice of the present invention, liquid sodium silicate or potassium silicate is added to ion milled water with ion-exchanged water in a milling tank, and then stirred by adding liquid lithium silicate, followed by methyltrimethoxysilane and methyl. Hydrolysis to add a reactive silane such as triethoxysilane, triethoxy vinylsilane, diphenyldimethoxysilane, triethoxysilane and the like to stir at least about 10 minutes at about 500 RPM until complete hydrolysis to obtain a silicate solution (binder) Steps;

The agitator speed was increased to about 2000 RPM in the hydrolyzed silicate solution, and a viscosity modifier of alumina sol or silica sol having a colloidal particle size of 40 to 180 nm of alumina or silica was slowly added to stabilize the viscosity. A viscosity adjusting step of stirring until the viscosity adjusting agent is completely hydrated;

In the viscosity control step, the viscosity is stabilized and the filler is made of silica or liquor in a state in which the viscosity modifier of alumina sol or silica sol is hydrated, and zinc oxide, tuff, diatomaceous earth, silicaka fume or metakaolin under the operation of the dust control equipment. Pozolan and granulated silicone rubber, fluorine resin, polystyrene, polyacryl or polysulfone beads, which are granular particles having a particle size of 0.1 to 20 microns (μ), were added and stirred and milled at 1000 RPM for at least 30 minutes. (μ) a wetting step of obtaining a water-resistant silicate-based inorganic binder by stirring at least 10 minutes by adding an additive which is a liquid wetting agent after adjusting the speed to 300 RPM after checking the following;

To the water-resistant silicate inorganic binder (liquid silicate solution) obtained through the wetting step Hiding power reinforcing step of stirring and milling at 1000 RPM for at least 30 minutes by adding silica under the operation of the dust control equipment;

A aging step of stirring the water-resistant silicate-based inorganic binder (liquid silicate solution) that has undergone the silver pen reinforcement step until the viscosity is stabilized, and then stabilizing the polymer beads and silica to react with the hydrated alumina sol or silica sol;

In the commercialization step of completing the water-resistant silicate-based inorganic binder by adjusting the viscosity by adding ion-exchange water to the water-resistant silicate-based inorganic binder (liquid silicate solution) after the aging step, the polymer beads 10 ~ 25% by weight , 20 to 45% by weight of liquid sodium silicate or potassium potassium silicate, 5 to 25% by weight of ion-exchanged water, 5 to 20% by weight of liquid lithium silicate, 1 to 5% by weight of reactive silane, 3 to 7% by weight of zinc oxide, pozzolane 3-10% by weight, 5-15% by weight of viscosity modifier of silica sol or alumina sol, 5.5-20% by weight of silica and 0.5-5% by weight of liquid wetting agent Obtain a binder.

In the case of the liquid sodium silicate used in the hydrolysis step, the molar ratio of SiO ₂ / Na ₂ O is preferably 2.8 to 3.4 and the liquid potassium silicate is preferably applied at a molar ratio of SiO ₂ / K ₂ O of 3.2 to 3.6.

Liquid silicates, which have a relatively high molar ratio, can shorten the time to initial dry contact and can be converted from a low viscosity state such as water to a semi-solid state even with a small amount of water evaporation.However, liquid silicates having a low molar ratio have high alkalinity. Due to its high affinity with water, the evaporation of moisture takes place slowly and heating at high temperature is required to achieve the desired curing state, or the viscosity is too high, making it difficult to mix with other materials and lacking flexibility, thus making practical application difficult. On the contrary, when the molar ratio of potassium silicate is too high, it exhibits extremely low viscosity, which makes it difficult to use practically.

The reactive silane used in the hydrolysis step is hydrolyzed to induce a reaction between alumina sol or silica sol and silica, and polymer beads and increase the surface strength after hardening the final silicate inorganic binder and inorganic binder. It helps to facilitate the mixing with the pigment when manufacturing as a paint.

The reactive silane may be methyltrimethoysilane, methyltriethoysilane, triethoyvinylsilane, diphenylimethoysilane, or triethoysilane. Add 1 to 5% by weight.

If less than 1% by weight, the reactivity between alumina sol or silica sol and silica, polymer beads is less than 5% by weight of the silicate inorganic binder after curing the surface strength is lowered.

The liquid lithium silicate serves to provide excellent waterproofing effect by helping the reactivity of the reactive silane and increasing the surface strength during curing, and 5 to 20% by weight is used.

If it is less than 5% by weight, the reactivity between the components is reduced, and if more than 20% by weight of the product is less economical.

The alumina sol or silica sol is suitable for the colloidal particle size of the alumina or silica 40 ~ 180nm, serves to adjust the viscosity of the inorganic binder and impart long-term stability and 5 to 15% by weight.

If it is less than 5% by weight, long-term stability is lowered. If it is more than 15% by weight, it becomes difficult to stir due to high viscosity.

The zinc oxide is used in 3 ~ 7% by weight as a curing agent and is easily affinity with the silicate to improve the hardness of the coating film, and in particular, assists in the complete removal of moisture by acting as an assistant to easily trap the carbon dioxide in the air to dry the coating quickly. When zinc ions are applied to metal surfaces such as steel, zinc-like coatings are formed, which enhances corrosion prevention, rust prevention and overall water resistance.

The pozzolanic can be used natural tuff, diatomaceous earth, volcanic ash and artificial pozzolane metakaolin, fly ash, silica gel fume, etc. 3 to 10% by weight is added to the pozzolanic reaction to improve the durability and seawater resistance, chemical resistance of the film And have anionic release, antifungal and antibacterial effects.

The polymer beads are silicon rubber, fluorine resin, polystyrene, polyacryl, polysulfone beads having a particle size of 0.1 to 20 microns (μ) and form a protective film having a fine structure to solve the weak water resistance defect of the liquid silicate binder. At the same time, it acts to increase the surface strength and flexibility of the coating, and 10 to 25% by weight is used.

In the case of the polymer beads, it is preferable to use emulsion polymerized beads to improve compatibility with water and to improve dispersibility. In the case of beads by chemical curing, heat resistance and hydrophobicity are improved.

In the case of the fluorine resin beads, beads obtained by the decomposition process by radiation such as electron beam irradiation and gamma ray irradiation may be used in addition to emulsion polymerization.

The silica is used in the 5.5 ~ 20% by weight, when less than 5.5% by weight is less concealed and when more than 20% by weight, the viscosity rises rapidly, making it difficult to stir.

The liquid wetting agent is composed of a liquid antifoaming agent and a dispersant to add 0.5 to 5% by weight, when less than 0.5% by weight, the dispersibility is deteriorated and bubbles are generated, when the 5% by weight or more the coating film is less dense.

The ion exchange water is used 5 to 25% by weight for viscosity control.

Looking at the manufacturing method of the water-resistant silicate-based inorganic binder (liquid silicate solution) having a fine structure of the polymer beads at the time of curing according to the present invention in more detail, the following examples are described.

TABLE 1 Basic Properties of Liquid Sodium Silicate, Potassium Silicate and Lithium Silicate

Hereinafter, the present invention will be described in more detail with reference to examples.

However, the scope of the present invention is not limited only to the illustrated embodiment.

The components described in <Table 2> were mixed at the respective mixing ratios using a mixer to prepare a binder in the following process.

            Table 2 Examples of Binder Composition and Preparation

After adding liquid sodium silicate or potassium silicate with ion-exchanged water to a conventional mill mixing tank and stirring it sufficiently, liquid lithium silicate is added and stirred, and stirred at about 500 RPM for at least 10 minutes until fully hydrolyzed by adding reactive silane. Raise the stirrer speed to about 2000RPM and sequentially add alumina sol (or silica sol), zinc oxide, pozzolane and polymer beads, and stir mill at 1000 RPM for 30 minutes or more and check the particle size with 20 micron (μ) or less and adjust the speed to 300 RPM. After the addition of a filler made of silica or fat sugar, the liquid wetting agent is added to complete the preparation.

The performance of the paint prepared according to the Examples is evaluated according to the following various functional test methods.

The binder of Examples 1 to 3 in Table 1 was coated with a brush or coated with an airless spray, dried and cured at room temperature, respectively, on the surface of an EGI sheet having a width of 150 mm, a length of 75 mm, and a thickness of 0.8 mm. Post washability, pencil hardness, stain resistance, base resistance, saline resistance, and dryness were measured and the physical properties of the binder run were summarized in <Table 2>.

(1) Wash resistance test Reciprocating wear recovery test according to the emulsion synthetic resin internal standard of KS M 5000 3351.

(2) Pencil hardness measurement, pencil hardness using a conventional pencil hardness tester (manufactured by Misubishi).

(3) Pollution resistance measurement Test of soot generated from burning petroleum and carbide on the surface of coating film, and then left for 1 day, and then removing contaminants on the specimen with water flowing at room temperature.

(4) Measure dry drying time, solidification drying time, and complete drying time, respectively, but touch drying time measures the time when it is not buried by touching the surface by hand, and solidification drying time can be rubbed by hand. Measure the time when it doesn't come out and measure the time when the binder doesn't come out by rubbing the surface more than 200 times with cotton soaked in water.

         TABLE 3 Physical Properties of Binder Implementation

             <Table 4> Measurement result of each experiment according to the experiment example

As shown in <Table 3> and <Table 4>, the silicate crab inorganic binder (liquid silicate solution) of the embodiment according to the present invention has excellent surface strength, washing resistance, fouling resistance and adhesiveness to prevent cracking of the coating film during curing. In addition, it can be confirmed that anion release, antibacterial, antibacterial, non-combustible and volatile organic compounds can be minimized.

Figure 2 shows an electron micrograph of the polymer beads used in the present invention, Figure 3 shows that the interface of the silicate inorganic binder (liquid silicate solution) after the curing using silicone rubber and polyacryl beads is dense and firm have.

The present invention has been filed as a result of the development of "Silicate-based inorganic aqueous binder", which is a technical development task of the SMEs technological innovation development project implemented by the Small and Medium Business Administration.

In the present invention, the final coating prepared using an inorganic binder (liquid silicate solution) having various properties besides water resistance has excellent paintability on various materials throughout the industry, and can secure overall physical and chemical properties. It can be widely used in industrial construction, building, civil engineering, marine, shipbuilding as well as household.

Claims (5)

Liquid sodium silicate or potassium silicate is added to the mill mixing tank with ion-exchanged water, and the mixture is sufficiently stirred. Then, liquid lithium silicate is added and stirred, followed by methyltrimethoxysilane, methyltriethoxysilane, triethoxyvinylsilane and di A hydrolysis step of adding a reactive silane such as phenyldimethoxysilane and triethoxysilane to a silicate solution by stirring at least about 500 minutes until it is completely hydrolyzed;
Viscosity control to increase the stirrer speed to about 2000RPM to the silicate solution after the hydrolysis step to slowly add a viscosity regulator of alumina sol or silica sol until the viscosity is stabilized and the viscosity regulator of alumina sol or silica sol is fully hydrated Steps;
In the viscosity control step, the viscosity is stabilized, and the viscosity control agent made of alumina sol or silica sol is hydrated, and under the operation of the dust control equipment, zinc oxide, tuff, diatomaceous earth, pozzolan and polymer beads made of silicaca fume or metakaolin are added and 1000 RPM After stirring for 30 minutes or more, check the particle size less than 20, adjust the speed to 300RPM, add a filler made of silica or fat, and add a liquid wetting agent to stir for 10 minutes or more to prepare a water-resistant silicate-based inorganic binder (liquid silicate solution). A wetting step obtained;
To the water-resistant silicate inorganic binder (liquid silicate solution) obtained through the wetting step Hiding power reinforcing step of stirring and milling at 1000 RPM for at least 30 minutes by adding silica under the operation of the dust control equipment;
A aging step of stirring the water-resistant silicate-based inorganic binder (liquid silicate solution) that has undergone the silver pen reinforcement step until the viscosity is stabilized, and then stabilizing the polymer beads and silica to react with the hydrated alumina sol or silica sol;
It is made of a commercialization step of completing the water-resistant silicate-based inorganic binder (liquid silicate solution) by adjusting the viscosity by adding ion-exchange water to the water-soluble silicate-based inorganic binder (liquid silicate solution) after the aging step to suit the purpose of use Method of producing a water-resistant silicate inorganic binder having a fine structure of the polymer beads at the time of curing.
The composition of the water-resistant silicate inorganic binder (liquid silicate solution) is 10 to 25% by weight of polymer beads, 20 to 45% by weight of liquid sodium silicate or liquid potassium silicate, 5 to 25% by weight of ion-exchanged water, and 5 to 20% of liquid lithium silicate. % By weight, 1 to 5% by weight of reactive silane, 3 to 7% by weight of zinc oxide, 3 to 10% by weight of pozzolane, 5 to 15% by weight of silica sol or alumina sol, 5.5 to 20% by weight of silica and 0.5 to 5% of liquid wetting agent Water-resistant silicate-based inorganic binder having a fine structure of the polymer beads when cured, characterized in that the composition in%.
The method of claim 1,
The alumina sol or silica sol is a method of producing a water-resistant silicate-based inorganic binder having a fine structure of the polymer beads at the time of curing, characterized in that the colloidal particle size of the alumina or silica is 40 ~ 180nm.
The method of claim 1,
The polymer beads have a fine structure of polymer beads upon curing, characterized in that any one of granular silicone rubber, fluorine resin, polystyrene, polyacryl or polysulfone beads having a particle size of 0.1-20 microns (μ) is independently made. Method for producing a water-resistant silicate inorganic binder having a.
The method of claim 1,
The polymer beads are water-resistant having a fine structure of the polymer beads upon curing, characterized by kneading silicon particles, fluororesins, polystyrenes, polyacryl or polysulfone beads, which are granular particles having a particle size of 0.1 to 20 microns (μ). Method for producing silicate inorganic binder.

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