KR102738602B1 - Multifunctional organic-inorganic composite waterproofing and anti-corrosion composition and waterproofing construction method for concrete structures using the same - Google Patents

Abstract

The present invention relates to a multifunctional organic-inorganic composite waterproofing composition and a waterproofing construction method of a concrete structure using the same. More specifically, one embodiment of the present invention is a waterproofing composition containing 10 to 30 wt% of an epoxy resin, 20 to 70 wt% of a filler, 0.5 to 10 wt% of a performance-improving additive, 5 to 20 wt% of a reactive diluent, and 8 to 25 wt% of a hardener; wherein the filler contains 100 parts by weight of calcium carbonate, 20 to 50 parts by weight of paramylon-containing fiber, and 1 to 10 parts by weight of cristobalite; The above performance-improving additive contains 100 parts by weight of polyoxyethylene polyoxypropylene monobutyl ether, 20 to 50 parts by weight of an epoxy compound of the following chemical formula 1, 1 to 10 parts by weight of a cashew nut shell liquid phenolic resin, and 1 to 10 parts by weight of a boric acid ester compound; the curing agent is an aromatic amine curing agent alone or a mixture of an aromatic amine curing agent and a thiol curing agent; and the paramylon-containing fiber contains 85 to 98 wt% of a polypropylene resin, 0.1 to 5 wt% of maleic anhydride, and 1 to 10 wt% of paramylon, thereby:
The present invention relates to a multifunctional organic-inorganic composite waterproofing and corrosion-resistant composition which not only reduces deterioration but also has excellent bonding strength with the concrete surface, and improves the mechanical properties of concrete structures such as waterproofing and water-repellent function, water resistance, chemical resistance, corrosion resistance, heat resistance, and weather resistance, and can shorten the construction period and achieve a cost-saving effect by being able to construct the adherend in a wet state as it is a room temperature curing type, and improves the elasticity and flexibility of the coating film so that the integral behavior performance in response to surface expansion and contraction caused by environmental changes (temperature, humidity, etc.) is improved, thereby suppressing the occurrence of cracks, deformation, peeling, etc., and can block corrosion and other deterioration factors of concrete structures to enhance durability, and a method for constructing a waterproofing and corrosion-resistant concrete structure using the same.
[Chemical Formula 1]

(In the equation, n is an integer of 0 or 1)

Description

{Multifunctional organic-inorganic composite waterproofing and anti-corrosion composition and waterproofing construction method for concrete structures using the same}

The present invention relates to a multifunctional organic-inorganic composite waterproofing and corrosion-resistant composition and a method for constructing a waterproofing and corrosion-resistant concrete structure using the same, which not only reduces deterioration but also has excellent bonding strength with the surface of concrete, and improves the mechanical properties of a concrete structure, such as waterproofing and water-repellent function, water resistance, chemical resistance, corrosion resistance, heat resistance, and weather resistance, and is a room temperature curing type, so that construction is possible even when the adherend is in a wet state, and the elasticity and flexibility of the coating are improved, so that the integral behavior performance corresponding to surface expansion and contraction caused by environmental changes (temperature, humidity, etc.) is improved, thereby suppressing the occurrence of cracks, deformation, peeling, etc.

Concrete structures are increasingly exposed to deteriorating factors such as drought or heavy rain caused by abnormal climate change, gaseous deteriorating factors such as SO _x , NO _{x ,} and CO ₂ , saline air in coastal areas, and salt compounds such as salt (NaCl) and calcium chloride (CaCl ₂ ), which are ingredients in winter deicing agents.

It is known that concrete structures exposed to these deterioration factors experience a decline in their performance due to deterioration mechanisms such as chloride attack, carbonation, alkali-aggregate reaction, and freeze-thaw. Specifically, when concrete structures are damaged by freeze-thaw, chloride attack, neutralization, chemicals, etc., voids are formed and cracks occur inside the concrete, which reduces strength, causes corrosion of reinforcing bars by penetrating water, and reduces durability, thereby preventing the concrete structure from performing its intended function.

Methods to reduce this deterioration phenomenon and protect the surface of concrete structures are largely divided into penetrating methods and coating methods.

The above-mentioned penetration method used materials manufactured by adding various solvents to silane and silicone resins. However, since the chemical reaction mainly occurred on the surface without penetrating deeply into the concrete, the durability, waterproofness, and weather resistance of the bond were not secured, so the protective performance was insufficient, and problems such as a poor working environment occurred due to the smell of the organic solvent added in a closed space.

In addition, the coating method generally mainly uses paints made of organic components such as epoxy, urethane, and acrylic resin paints. Paints made of organic components have the advantages of good processability, excellent adhesion, and flexibility. However, the construction cost is very high, and there is a possibility that the adhesion to the concrete surface is reduced, oxidation and aging occur due to cutting of carbon chains by ultraviolet rays, lifting phenomenon due to movement of moisture on the concrete surface, construction difficulty, environmental pollution due to the use of organic solvents, and safety problems may occur. In addition, there is a problem that durability is reduced due to easy deterioration by ultraviolet rays, ozone, or moisture, heat resistance is low, and organic substances such as oil are easily mixed in, causing contamination. In addition, the coating material of organic components does not harden when the surface moisture content of concrete exceeds 8%, so the surface must be completely dried, which increases the construction period, and since the coefficient of thermal expansion is different from that of concrete, it is difficult to move at all, and peeling and peeling of the coating layer are likely to occur over a long period of time.

In addition, organic and inorganic waterproofing agents are being produced and sold as waterproofing methods for concrete structures. However, in the case of inorganic agents, since water glass is the main ingredient, there are problems in that when there is moisture, such as in underground structures, it may be dissolved and lose its waterproofing properties, and when mixed into concrete, the total alkali content increases, which has a fatal effect on the durability of the concrete. In addition, in the case of organic agents, most of them are organic silicon emulsified in water, which has the problem that it is very difficult to disperse inside the concrete.

Republic of Korea Patent No. 10-2261593 Republic of Korea Patent No. 10-1780705 Republic of Korea Patent No. 10-1971118

The present invention has been made to solve the above-described problems, and one embodiment of the present invention provides a multifunctional organic-inorganic composite waterproofing composition that reduces deterioration caused by temperature, humidity, ultraviolet rays, ozone or carbon dioxide in the atmosphere, other pollutants, and improves the basic properties of concrete structures such as waterproofing and water-repellent functions, as well as improving adhesion to a concrete surface and all-round behavioral performance in response to surface elasticity, and a method for constructing a waterproofing method for concrete structures using the same.

The various problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

One embodiment of the present invention is a waterproofing composition containing 10 to 30 wt% of an epoxy resin, 20 to 70 wt% of a filler, 0.5 to 10 wt% of a performance-improving additive, 5 to 20 wt% of a reactive diluent, and 8 to 25 wt% of a curing agent;

The above filler contains 100 parts by weight of calcium carbonate, 20 to 50 parts by weight of paramylon-containing fibers, and 1 to 10 parts by weight of cristobalite;

The above performance-improving additive contains 100 parts by weight of polyoxyethylene polyoxypropylene monobutyl ether, 20 to 50 parts by weight of an epoxy compound of the following chemical formula 1, 1 to 10 parts by weight of a cashew nut shell liquid phenolic resin, and 1 to 10 parts by weight of a boric acid ester compound;

The above curing agent is an aromatic amine curing agent alone or a mixture of an aromatic amine curing agent and a thiol curing agent;

The above paramylon-containing fiber provides a multifunctional organic-inorganic composite waterproofing/corrosion-resistant composition containing 85 to 98 wt% of polypropylene resin, 0.1 to 5 wt% of maleic anhydride, and 1 to 10 wt% of paramylon.

[Chemical Formula 1]

(In the equation, n is an integer of 0 or 1)

The above paramylon-containing fibers

It is a paramylon-containing fiber having a resorcinol-formaldehyde-latex layer formed;

The paramylon-containing fiber having the resorcinol-formaldehyde-latex layer formed thereon is manufactured by a method including the steps of mixing 100 parts by weight of paramylon-containing fiber and 1 to 20 parts by weight of avicularin and then drying the mixture, immersing the mixture in 90 to 120 parts by weight of a resorcinol-formaldehyde-latex solution to manufacture an immersion product, and drying the immersion product and then heating it at 80 to 100° C. to manufacture the paramylon-containing fiber having the resorcinol-formaldehyde-latex layer formed thereon;

The above resorcinol-formaldehyde-latex solution may have a molar ratio of resorcinol and formaldehyde of 1:1 to 3, and may contain 10 to 30 parts by weight of latex per 1 part by weight of the total content of resorcinol and formaldehyde.

The above cristobalite

The surface is cristobalite treated with IPL;

The above IPL treatment may be performed under conditions where the voltage is 1000 to 1400 V, the exposure time is 1 to 10 ms, and the frequency is 0.1 to 10 Hz.

The above performance improving additives

It may further contain 1 to 10 parts by weight of Cedrol per 100 parts by weight of polyoxyethylene polyoxypropylene monobutyl ether.

The above performance improving additives

Further containing 1 to 10 parts by weight of a methylene malonate compound per 100 parts by weight of polyoxyethylene polyoxypropylene monobutyl ether;

The above methylene malonate compound may be at least one selected from the group consisting of diethyl ethoxymethylene malonate, diethyl aminomethylene malonate, and dimethyl methylene malonate.

In addition, another embodiment of the present invention is a method for constructing a waterproofing method for a concrete structure using the multifunctional organic-inorganic composite waterproofing composition,

The method may include: a step of cleaning the laitance, impurities or deteriorated areas of a concrete structure by chipping and cleaning, and then cleaning the resulting cracks, grooves or deteriorated areas using a quick-hardening putty; a step of applying a modified liquid silicate-based penetrating concrete reinforcing agent to the cleaned surface to form a concrete reinforcing layer; a step of applying a primer to the concrete reinforcing layer to form a primer layer; and a step of applying the multifunctional organic-inorganic composite waterproofing and corrosion-resistant composition to the formed primer layer to form a waterproofing and corrosion-resistant layer.

According to a multifunctional organic-inorganic composite waterproofing and corrosion-resistant material composition according to one embodiment of the present invention and a method for waterproofing and corrosion-resistant construction of a concrete structure using the same, not only is the deterioration phenomenon caused by temperature, humidity, ultraviolet rays, ozone or atmospheric carbon dioxide, and other pollutants reduced, but also the adhesion strength with the concrete surface is excellent, and the mechanical properties of the concrete structure, such as waterproofing and water-repellent function, water resistance, chemical resistance, corrosion resistance, heat resistance, and weather resistance, are improved, and since it is a room temperature curing type, construction is possible even when the adherend is in a wet state, so that the construction period can be shortened, thereby achieving the effect of reducing costs. In addition, since the elasticity and flexibility of the coating film are improved, the integral behavior performance in response to the expansion and contraction of the surface caused by environmental changes (temperature, humidity, etc.) is improved, so that the occurrence of cracks, deformation, and peeling can be suppressed, and corrosion and other deterioration factors of the concrete structure are blocked, thereby increasing the durability.

In addition, according to a multifunctional organic-inorganic composite waterproofing composition according to one embodiment of the present invention and a method for constructing a waterproofing method for a concrete structure using the same, a concrete reinforcing layer is formed using a modified liquid silicate-based penetrating concrete reinforcing agent, and then the multifunctional organic-inorganic composite waterproofing composition is applied, thereby having the effect of densifying the internal structure through penetration into the concrete, blocking pores, and improving the bond strength with the concrete surface.

Figures 1 and 2 each illustrate a schematic construction sequence diagram of a method for waterproofing a concrete structure using a multifunctional organic-inorganic composite waterproofing composition according to various embodiments of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples, and the present invention is not limited thereby, and the present invention is defined only by the scope of the claims described below.

One embodiment of the present invention is a waterproofing composition containing 10 to 30 wt% of an epoxy resin, 20 to 70 wt% of a filler, 0.5 to 10 wt% of a performance-improving additive, 5 to 20 wt% of a reactive diluent, and 8 to 25 wt% of a curing agent;

The above filler contains 100 parts by weight of calcium carbonate, 20 to 50 parts by weight of paramylon-containing fibers, and 1 to 10 parts by weight of cristobalite;

The above performance-improving additive contains 100 parts by weight of polyoxyethylene polyoxypropylene monobutyl ether, 20 to 50 parts by weight of an epoxy compound of the following chemical formula 1, 1 to 10 parts by weight of a cashew nut shell liquid phenolic resin, and 1 to 10 parts by weight of a boric acid ester compound;

The above curing agent is an aromatic amine curing agent alone or a mixture of an aromatic amine curing agent and a thiol curing agent;

The above paramylon-containing fiber provides a multifunctional organic-inorganic composite waterproofing/corrosion-resistant composition containing 85 to 98 wt% of polypropylene resin, 0.1 to 5 wt% of maleic anhydride, and 1 to 10 wt% of paramylon.

[Chemical Formula 1]

(In the equation, n is an integer of 0 or 1)

According to a multifunctional organic-inorganic composite waterproofing and corrosion-resistant material composition according to one embodiment of the present invention and a method for waterproofing and corrosion-resistant construction of a concrete structure using the same, not only is the deterioration phenomenon caused by temperature, humidity, ultraviolet rays, ozone or atmospheric carbon dioxide, and other pollutants reduced, but also the adhesion strength with the concrete surface is excellent, and the mechanical properties of the concrete structure, such as waterproofing and water-repellent function, water resistance, chemical resistance, corrosion resistance, heat resistance, and weather resistance, are improved, and since it is a room temperature curing type, construction is possible even when the adherend is in a wet state, so that the construction period can be shortened, thereby achieving the effect of reducing costs. In addition, since the elasticity and flexibility of the coating film are improved, the integral behavior performance in response to the expansion and contraction of the surface caused by environmental changes (temperature, humidity, etc.) is improved, so that the occurrence of cracks, deformation, and peeling can be suppressed, and corrosion and other deterioration factors of the concrete structure are blocked, thereby increasing the durability. In addition, according to a multifunctional organic-inorganic composite waterproofing composition according to one embodiment of the present invention and a method for constructing a waterproofing method for a concrete structure using the same, a concrete reinforcing layer is formed using a modified liquid silicate-based penetrating concrete reinforcing agent, and then the multifunctional organic-inorganic composite waterproofing composition is applied, thereby having the effect of densifying the internal structure through penetration into the concrete, blocking pores, and improving the bond strength with the concrete surface.

Hereinafter, a multifunctional organic-inorganic composite waterproofing composition according to one embodiment of the present invention will be examined in more detail.

A multifunctional organic-inorganic composite waterproofing composition according to one embodiment of the present invention contains 10 to 30 wt% of an epoxy resin, 20 to 70 wt% of a filler, 0.5 to 10 wt% of a performance-improving additive, 5 to 20 wt% of a reactive diluent, and 8 to 25 wt% of a curing agent.

The epoxy resin contained in the present invention is an epoxy resin having a solid content generally used in the field, and specifically, at least one epoxy resin selected from glycidyl ether-based epoxy resin, glycidyl ester-based epoxy resin, bisphenol A-type epoxy resin, and bisphenol F-type epoxy resin can be used.

In addition, it is preferable that the epoxy resin has an epoxy equivalent of 160 to 250 g/eq and a viscosity of 10,000 to 20,000 cps at 25° C. The epoxy resin exhibits excellent coating film strength, toughness, high-temperature characteristics, chemical resistance, and water resistance, and does not generate volatile substances or shrink in volume during curing, and plays a role in improving the bond strength with concrete structures, waterproofing, water-reinforcing properties, and thermal elasticity.

Considering the above-mentioned improvement effect, the epoxy resin may be contained in the multifunctional organic-inorganic composite waterproofing/protection material composition of the present invention in an amount of 10 to 30 wt%.

The filler contained in the present invention fills the pores in the coating film and improves strength reinforcing performance such as excellent tensile performance and gloss, as well as ductility, impact resistance, wear resistance, water resistance, chemical resistance, corrosion resistance, crack resistance, freeze-thaw resistance, chloride ion penetration resistance, heat resistance, and weather resistance.

The above filler may be contained in the multifunctional organic-inorganic composite waterproofing/corrosion-resistant composition of the present invention in an amount ranging from 20 to 70 wt%. If it is contained in an amount less than the above range, there is a problem that the physical properties may be deteriorated due to effects on hardness, tear strength, etc., and if it exceeds the above range, there is a problem that the viscosity may increase and the flowability may be affected, resulting in deterioration of the mechanical properties.

More specifically, the filler may preferably be one containing 100 parts by weight of calcium carbonate, 20 to 50 parts by weight of paramylon-containing fibers, and 1 to 10 parts by weight of cristobalite.

The above calcium carbonate has the function of improving dimensional stability, impact resistance, chemical resistance, and resistance to chloride ion penetration.

Hereinafter, the contents of other components constituting the filler are based on 100 parts by weight of the calcium carbonate.

The above paramylon-containing fiber preferably contains 85 to 98 wt% of polypropylene resin, 0.1 to 5 wt% of maleic anhydride, and 1 to 10 wt% of paramylon. The paramylon-containing fiber is dispersed in the waterproofing and corrosion-resistant composition to not only prevent shrinkage and cracking, but also serve to reinforce mechanical and chemical properties such as corrosion resistance, friction resistance, heat resistance, and durability of the coating film. Specifically, maleic anhydride blended within the above range is contained in the polypropylene resin having excellent mechanical and chemical properties to impart hydrophilicity, thereby improving clumping between fibers and enhancing adhesion. In addition, paramylon further enhances the properties of the reinforcing fiber by preventing shrinkage and cracking and improving corrosion resistance and durability. The paramylon-containing fiber preferably has a length of 20 to 50 mm and a diameter of 1 to 3 mm.

These paramylon-containing fibers can be manufactured by conventional methods of melting, spinning, drawing, heat treatment, and cutting. Specifically, considering workability and fiber properties, the melting temperature is preferably 20 to 60°C, the drawing can be fiberized using a partial orientation-drawing/twisting method or a direct spinning drawing method at a temperature of 70 to 120°C, and the heat treatment is preferably 40 to 200°C.

In addition, the paramylon-containing fiber may be a paramylon-containing fiber having a resorcinol-formaldehyde-latex layer formed thereon. The paramylon-containing fiber having the resorcinol-formaldehyde-latex layer formed thereon not only functions as the reinforcing fiber, but also has excellent light resistance because its properties do not change easily when exposed to light, and plays a role in improving light shock and thermal shock resistance, such as increasing light discoloration resistance and corrosion resistance. In addition, it plays a role in preventing wear-resistant microcracks and improving salt damage and freeze-thaw resistance.

Specifically, the paramylon-containing fiber having the resorcinol-formaldehyde-latex layer formed thereon can be manufactured by a method including the steps of mixing 100 parts by weight of a paramylon-containing fiber and 1 to 20 parts by weight of avicularin and then drying the mixture, immersing the mixture in 90 to 120 parts by weight of a resorcinol-formaldehyde-latex solution to manufacture an immersion product, and drying the immersion product and then heating it at 80 to 100° C. to manufacture the paramylon-containing fiber having the resorcinol-formaldehyde-latex layer formed thereon.

At this time, it is preferable that the resorcinol-formaldehyde-latex solution has a molar ratio of resorcinol and formaldehyde of 1:1 to 3, and that the latex is 10 to 30 parts by weight per 1 part by weight of the total content of resorcinol and formaldehyde. The avicularin uniformly forms a resorcinol-formaldehyde-latex layer on the paramylon-containing fiber, while at the same time enhancing the tensile strength and improving durability and wear resistance.

The above latex is generally used in the field and is not particularly limited, but may be at least one selected from the group consisting of XSBR latex (carboxylated styrene-butadiene copolymer), HSSBR latex (styrene-butadiene copolymer), NBR latex (nitrile-butadiene copolymer), CR latex (polychloroprene), PSBR latex (pyridine-styrene-butadiene copolymer), and styrene-butadiene-vinylpyridine copolymer latex.

In addition, the paramylon-containing fiber may be a surface-treated paramylon-containing fiber irradiated with an E-beam in air at an irradiation dose of 50 to 500 kGy. The surface-treated paramylon-containing fiber can induce a chemical reaction on the surface to improve the bonding strength with resorcinol-formaldehyde-latex. At this time, if the irradiation dose of the E-beam is less than the above range, there is a problem that it is difficult to induce a chemical reaction on the surface of the paramylon-containing fiber, and if it exceeds the above range, not only does excessive energy deteriorate the properties of the carbon fiber, but also the surface is not sufficiently treated compared to the irradiation dose, which is economically disadvantageous.

It is preferable that the paramylon-containing fibers be contained in an amount of 20 to 50 parts by weight per 100 parts by weight of the calcium carbonate. If the content of the paramylon-containing fibers is too low, there is a problem that the above-mentioned improvement effect may be insufficient, and if the content of the paramylon-containing fibers is too high, there is a problem that strength properties such as compressive strength may be reduced or price competitiveness may be reduced.

The above cristobalite has the function of improving thermal and physical strength, preventing wear and tear, and improving corrosion resistance, weather resistance and gloss, and prevents the coating from being painted or deteriorated due to long-term exposure to high temperatures.

In addition, the cristobalite improves the miscibility and dispersibility with other components in the composition, thereby further improving the above-mentioned effect, and in order to improve chemical resistance and wear resistance, it is preferable to use cristobalite whose surface has been IPL-treated by irradiating the cristobalite surface with IPL (Intense Pulse Light). At this time, the IPL irradiation is not particularly limited as it is generally used in the relevant field, and specifically, it is preferable to perform the IPL irradiation under the conditions of a voltage of 1000 to 1400 V, an exposure time of 1 to 10 ms, and a frequency of 0.1 to 10 Hz.

It is preferable that the cristobalite be contained in an amount of 1 to 10 parts by weight relative to 100 parts by weight of the calcium carbonate. If the content of the cristobalite is too small, there is a problem that the improvement effect described above may be insufficient, and if the content of the cristobalite is too large, there is a problem that the unit price and viscosity increase, resulting in poor workability and inability to exhibit the desired properties.

The performance-improving additive contained in the present invention realizes excellent elongation and ductility, and plays a role in improving strength performance such as adhesive performance and tensile performance, impact resistance, water resistance, waterproofing and water-repellent function, chemical resistance, corrosion resistance, crack resistance, freeze-thaw resistance, chloride ion penetration resistance, heat resistance, and weather resistance.

These performance-improving additives may be contained in the multifunctional organic-inorganic composite waterproofing and corrosion-resistant composition of the present invention in an amount ranging from 0.5 to 10 wt%. If the amount is less than the above range, there is a problem that the above-mentioned improvement effect may be insufficient, and if the amount is more than the above range, there is a problem that the effect is no longer significantly improved and there is a concern that other physical properties of the final cured product may be deteriorated.

Specifically, the performance-improving additive contains 100 parts by weight of polyoxyethylene polyoxypropylene monobutyl ether, 20 to 50 parts by weight of the epoxy compound of the chemical formula 1, 1 to 10 parts by weight of cashew nut shell liquid phenolic resin, and 1 to 10 parts by weight of a boric acid ester compound.

The above polyoxyethylene polyoxypropylene monobutyl ether plays a role in improving the bonding strength with concrete structures, waterproofing and water-repellent functions, water resistance, heat resistance, and weather resistance.

Hereinafter, the contents of other components constituting the above performance-improving additive are based on 100 parts by weight of the above polyoxyethylene polyoxypropylene monobutyl ether.

The epoxy compound of the above chemical formula 1 improves the elasticity and flexibility of the coating film even in an environment where environmental changes (temperature, humidity, etc.) are repeated, thereby suppressing peeling and cracking, while improving heat resistance and wear resistance and enhancing storage stability.

It is preferable that the epoxy compound of the chemical formula 1 is included in an amount of 20 to 50 parts by weight per 100 parts by weight of polyoxyethylene polyoxypropylene monobutyl ether. If the content of the epoxy compound of the chemical formula 1 is too low, there is a problem that the above-mentioned improvement effect may be insufficient, and if the content of the epoxy compound of the chemical formula 1 is too high, there is a problem that price competitiveness may be reduced.

The above cashew modified phenol resin has excellent curing properties and exhibits excellent performance even in high humidity environments, implements excellent waterproofing and water repellent functions, and has excellent water resistance, flexibility, and compatibility with epoxy resins, as well as providing excellent corrosion and aging prevention effects.

The above cashew modified phenol resin is not particularly limited to those commonly used in the field, and for example, SP6700 (Schenectady Chemicals Inc.) can be used.

It is preferable that the cashew modified phenol resin is contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the polyoxyethylene polyoxypropylene monobutyl ether. If the content of the cashew modified phenol resin is too small, there is a problem that the above-mentioned improvement effect may be insufficient, and if the content of the cashew modified phenol resin is too large, it is difficult to expect any further improvement effect, and there is a problem that price competitiveness may be reduced.

The above boric acid ester compound not only improves chemical resistance, waterproofing and water-repellent functions, corrosion resistance, resistance to chloride ion penetration, and weather resistance, but also plays a role in improving the storage stability of the waterproofing and corrosion prevention composition.

The above boric acid ester compound may be at least one selected from the group consisting of trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate.

It is preferable that the boric acid ester compound is contained in an amount of 1 to 10 parts by weight per 100 parts by weight of the polyoxyethylene polyoxypropylene monobutyl ether. If the content of the boric acid ester compound is too small, there is a problem that the above-mentioned improvement effect may be insufficient, and if the content of the boric acid ester compound is too large, there is a problem that the workability and the smoothness of the coating film may be reduced.

In addition, the performance-improving additive may further contain 1 to 10 parts by weight of Cedrol per 100 parts by weight of polyoxyethylene polyoxypropylene monobutyl ether. The Cedrol improves the elasticity and flexibility of the coating film, and improves impact resistance, chemical resistance, and durability, thereby improving peeling and cracking.

In addition, the performance-improving additive may further contain 1 to 10 parts by weight of a methylene malonate compound per 100 parts by weight of polyoxyethylene polyoxypropylene monobutyl ether.

The above methylene malonate compound plays a role in improving crack resistance, heat resistance, chemical resistance, waterproofing and water-repellent function, corrosion resistance, freeze-thaw resistance, and weather resistance. The methylene malonate compound may be at least one selected from the group consisting of diethyl ethoxymethylene malonate, diethyl aminomethylene malonate, and dimethyl methylene malonate.

The reactive diluent contained in the present invention lowers viscosity, thereby improving workability in an environmentally friendly manner and enabling the composition to be effectively dispersed.

The above reactive diluent is not particularly limited as it is commonly used in the art, but may be at least one selected from the group consisting of butyl glycidyl ether (BGE), lauryl glycidyl ether (LGE), propylene glycol diglycidyl ether (PG-207P), 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether, for example.

Such reactive diluents may be contained in the multifunctional organic-inorganic composite waterproofing/corrosion-resistant composition of the present invention in an amount ranging from 5 to 20 wt%. If the amount is less than the above range, there is a problem that the effect of reducing viscosity may be insignificant and the curing speed may be significantly reduced. If the amount is more than the above range, there is a problem that the mechanical properties of the final cured product, such as hardness, may be reduced, making it difficult to obtain the desired properties.

Since the curing agent contained in the present invention affects the working time, curing time, and physical properties after curing depending on its type and amount, it is preferable to use an aromatic amine curing agent that can be applied to various surfaces. Considering the above-mentioned improvement effect, the curing agent may be contained in the multifunctional organic-inorganic composite waterproofing and corrosion-resistant material composition of the present invention in an amount of 8 to 25 wt%.

The above aromatic amine curing agent reacts with organic groups to increase cross-linking density, thereby improving surface hardness and adhesion and promoting curing.

At this time, the aromatic amine curing agent is preferably at least one selected from the group consisting of 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, and mixtures thereof; and the imidazole curing agent is preferably at least one selected from the group consisting of 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole, and mixtures thereof.

In addition, the curing agent of the present invention can be used in combination with the aromatic amine curing agent to further improve strength performance such as adhesive performance and tensile performance and to induce reaction of unreacted epoxy groups to enhance additional properties (elongation, ductility, waterproofing, water repellency, etc.). It is preferable to use the aromatic amine curing agent and the thiol curing agent in a weight ratio of 1:0.1 to 0.3. At this time, the thiol curing agent acts as an accelerator to promote the reaction with the aromatic amine curing agent by ring-opening polymerization reaction of the thiolate (-S'') of the reactive thiol (-SH) group with the epoxy group.

The above thiol-based curing agent may be at least one selected from the group consisting of tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), di-pentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), and tris(2-(mercaptopropionyl oxy)ethyl)isocyanate.

In addition, another embodiment of the present invention provides a method for constructing a waterproofing method for a concrete structure using the multifunctional organic-inorganic composite waterproofing composition, the method comprising the steps of: chipping and cleaning laitance, impurities or deteriorated areas of the concrete structure, and then organizing the resulting cracks, grooves or deteriorated areas using a fast-hardening putty; applying a modified liquid silicate-based penetrating concrete reinforcing agent to the organized surface to form a concrete reinforcing layer; applying a primer to the concrete reinforcing layer to form a primer layer; and applying the multifunctional organic-inorganic composite waterproofing composition to the formed primer layer to form a waterproofing layer.

A schematic construction sequence diagram of a method for waterproofing a concrete structure using a multifunctional organic-inorganic composite waterproofing composition according to various embodiments of the present invention is shown in Figures 1 and 2.

The above fast-hardening putty material is used to fill the pores of concrete and make the base surface flatter. Such fast-hardening putty material is commonly used in the relevant field and its type is not particularly limited. However, non-limiting examples of the fast-hardening putty material include epoxy-based, silicone-based, and acrylic-based putty materials.

In addition, the above-mentioned modified liquid silicate penetrating concrete reinforcing agent reacts with the concrete surface of the structure, densifies the internal structure through penetration into the concrete, blocks pores, reinforces and protects the strength such as adhesive performance and tensile performance with the concrete surface, and improves water resistance by inhibiting neutralization and aging of the concrete.

It is more preferable to use the modified liquid silicate-based penetrating concrete reinforcing agent containing 35 to 50 wt% of water, 45 to 60 wt% of a composite alkali silicate including sodium silicate, potassium silicate and lithium silicate, and 0.1 to 5 wt% of a fluorinated anionic surfactant.

More specifically, the composite alkali silicate may include 35 to 50 wt% of sodium silicate, 20 to 40 wt% of potassium silicate, and 15 to 30 wt% of lithium silicate.

In addition, the fluorinated anionic surfactant is generally used in the art and its type is not particularly limited. However, a non-limiting example of the fluorinated anionic surfactant may be a fluoroalkylated sulfonamide surfactant. A non-limiting example of the fluoroalkylated sulfonamide surfactant may be 3M™ Electronic Surfactant 4200.

In addition, the primer is used to facilitate the attachment of the waterproofing layer to the base surface, and the primer is generally used in the relevant field and its type is not particularly limited. However, non-limiting examples of the primer include a primer containing acrylic, acrylic-urethane, ethyl vinyl acetate (EVA), styrene-butadiene, etc. The primer layer can be formed to a thickness of 10 to 50 μm.

In addition, the step of forming the waterproofing layer can be performed by applying the multifunctional organic-inorganic composite waterproofing composition according to one embodiment of the present invention 1 to 5 times, and the waterproofing layer can be formed to a thickness of 100 to 600 μm by applying the composition once.

In addition, when the concrete structure is exposed to the ground and directly affected by the external environment, the waterproofing construction method of the concrete structure may further include a step of forming a surface protection layer for surface reinforcement by applying a surface protection agent for surface reinforcement after the step of forming the waterproofing layer. As a result, the durability, weather resistance, surface hardness, waterproofness, water resistance, neutralization prevention, and salt resistance of the concrete structure can be further improved. The surface protection agent for surface reinforcement is generally used in the relevant field and its type is not particularly limited. However, a non-limiting example of the surface protection agent for surface reinforcement is preferably one containing a solvent-free epoxy. In addition, the surface protection layer for surface reinforcement can be formed to a thickness of 200 to 800 μm.

According to a multifunctional organic-inorganic composite waterproofing and corrosion-resistant material composition according to one embodiment of the present invention and a method for waterproofing and corrosion-resistant construction of a concrete structure using the same, not only is the deterioration phenomenon caused by temperature, humidity, ultraviolet rays, ozone or atmospheric carbon dioxide, and other pollutants reduced, but also the adhesion strength with the concrete surface is excellent, and the mechanical properties of the concrete structure, such as waterproofing and water-repellent function, water resistance, chemical resistance, corrosion resistance, heat resistance, and weather resistance, are improved, and since it is a room temperature curing type, construction is possible even when the adherend is in a wet state, so that the construction period can be shortened, thereby achieving the effect of reducing costs. In addition, since the elasticity and flexibility of the coating film are improved, the integral behavior performance in response to the expansion and contraction of the surface caused by environmental changes (temperature, humidity, etc.) is improved, so that the occurrence of cracks, deformation, and peeling can be suppressed, and corrosion and other deterioration factors of the concrete structure are blocked, thereby increasing the durability. In addition, according to a multifunctional organic-inorganic composite waterproofing composition according to one embodiment of the present invention and a method for constructing a waterproofing method for a concrete structure using the same, a concrete reinforcing layer is formed using a modified liquid silicate-based penetrating concrete reinforcing agent, and then the multifunctional organic-inorganic composite waterproofing composition is applied, thereby having the effect of densifying the internal structure through penetration into the concrete, blocking pores, and improving the bond strength with the concrete surface.

Above, although preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various modifications are possible by a person having ordinary skill in the art within the scope of the technical idea of the present invention.

<Manufacturing Example 1> Fiber containing paramylon

90 wt% of polypropylene resin, 3 wt% of maleic anhydride, and 7 wt% of Paramylon (Euglena Co., Ltd.) were blended in an extruder, melted, and manufactured into fibers by a partial orientation-drawing/twisting method. At this time, the spinning speed was 1000 m/min to obtain a spun-tow. After that, the spun-tow was aged for 4 hours or more and then drawn (to a diameter of about 1.8 mm). At this time, the drawing temperature was 85°C and the drawing ratio was 3.4. After that, heat treatment was performed at 110°C and a rotary cutter was used to cut the fibers to a length of about 37 mm to manufacture Paramylon-containing fibers.

<Manufacturing Example 2> Paramylon-containing fiber with resorcinol-formaldehyde-latex layer formed

100 parts by weight of the paramylon-containing fiber of the above-mentioned Manufacturing Example 1 and 15 parts by weight of avicularin were mixed, and then dried at 60°C to prepare a mixture. Thereafter, the mixture was immersed in 110 parts by weight of a resorcinol-formaldehyde-latex solution to prepare an immersion product. At this time, the resorcinol-formaldehyde-latex solution has a molar ratio of resorcinol and formaldehyde of 1:2, and 20 parts by weight of latex (styrene-butadiene-vinylpyridine copolymer latex) was mixed for each 1 part by weight of the total content of resorcinol and formaldehyde. Thereafter, the immersion product was dried at 60°C and heated at 90°C to prepare a paramylon-containing fiber having a resorcinol-formaldehyde-latex layer formed thereon.

<Manufacturing Example 3> Paramylon-containing fiber with resorcinol-formaldehyde-latex layer formed

The same procedure as in Manufacturing Example 2 was followed, except that the paramylon-containing fiber of Manufacturing Example 1 was irradiated with E-beam at a dose of 200 kGy in air. Thereafter, the paramylon-containing fiber irradiated with the E-beam was placed in a three-necked flask, a vacuum was applied to remove air, and the surface-treated paramylon-containing fiber was used to manufacture a paramylon-containing fiber having a resorcinol-formaldehyde-latex layer formed thereon.

<Manufacturing Example 4> Cristobalite with IPL treatment on the surface

IPL (Intense Pulse Light) was irradiated on the surface of cristobalite to produce cristobalite with an IPL treatment on the surface. At this time, the IPL irradiation was performed under the conditions of a volume ratio of argon and oxygen of 9:1 and RT, with a voltage of 1100 V, an exposure time of 3 ms, and a frequency of 1 Hz, 60 times (20 times x 3 times).

<Examples and Comparative Examples>

A multifunctional organic-inorganic composite waterproofing composition and a comparative composition were prepared by stirring and mixing the ingredients and contents as shown in Table 1 below.

Classification (weight %) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Epoxy resin 24 24 24 24 24 Filler 35 35 35 39 35 Weight part Calcium carbonate 100 100 100 100 100 Zinc oxide - - - 30 30 Paramylon containing fiber [Manufacturing Example 1]30 [Manufacturing Example 2]
30 [Manufacturing Example 3]
30 - - Cristobalite 7 [Manufacturing Example 4]7 [Manufacturing Example 4]
7 - - Performance-enhancing additives 6 6 6 - 6 Weight part Polyoxyethylene polyoxypropylene monobutyl ether
(CAS No.: 9065-63-8) 100 100 100 - 100 Epoxy compound of chemical formula 1
(CELLOXIDE 2081 from Daicel Chemical Industries, Ltd.) 35 35 35 - - Cashew modified phenol resin 6 6 6 - - boric acid ester compounds 4 4 4 - - Cedrol - 3 3 - - Diethyl ethoxymethylene malonate - - 2 - - Reactive diluent (butyl glycidyl ether) 16 16 16 18 16 Hardener 19 19 19 19 19 Weight ratio 4,4'-Diaminodiphenylsulfone 1 1 1 1 1 Tris(3-mercaptopropionate) - 0.2 0.2 - - Epoxy Resin: Bisphenol A type epoxy resin, Kukdo Chemical Co., Ltd., KEM-019-50 product
Epoxy compound of chemical formula 1: n is 1
Cashew modified phenol resin: SP6700 (Schenectady Chemicals Inc.)
Boric acid ester compound: 1:1 weight ratio mixture of trimethyl borate and triisopropyl borate

Below, the experimental results comparing the characteristics of the multifunctional organic-inorganic composite waterproofing compositions manufactured according to Examples 1 to 3 of the present invention with the comparative compositions manufactured according to Comparative Examples 1 and 2 are presented so that the characteristics can be more easily understood.

<Example of an exam>

After producing a mortar test piece (50×50×50 mm) for performance evaluation, a modified liquid silicate-based penetrating concrete reinforcing agent was applied once. At this time, the modified liquid silicate-based penetrating concrete reinforcing agent was used in a mixture of 40 wt% of water, 58 wt% of a composite alkali silicate containing sodium silicate, potassium silicate, and lithium silicate in a weight ratio of 40:36:24, and 2 wt% of a fluorinated anionic surfactant (3M™ Electronic Surfactant 4200). Thereafter, the multifunctional organic-inorganic composite waterproofing compositions manufactured according to Examples 1 to 3 and the comparative compositions manufactured according to Comparative Examples 1 and 2 were applied once each to the mortar test specimens for performance evaluation to which the modified liquid silicate-based penetrating concrete reinforcing agent was applied. The mortar test specimens for performance evaluation were subjected to a property test of the coating film, and the results are shown in Table 2 below.

division Test method Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Appearance KS F 4929 No problem No problem No problem No problem No problem Bond strength (N/mm ² )_Standard 2.70 3.05 3.41 1.24 1.48 Bond strength (N/mm ² )_Absorption 2.51 2.72 3.37 1.03 1.08 Tensile strength (N/mm ² ) 20.1 20.6 21.2 8.1 10.5 Elongation rate (%) 11.1 11.8 12.1 3.3 5.6 Inner permeability No problem No problem No problem No problem No problem Flexibility No problem No problem No problem Crack occurrence No problem Low temperature high temperature repeated test No problem No problem No problem Crack occurrence The fine print Moisture resistance No problem No problem No problem Swelling
generation No problem Impact resistance No problem No problem No problem Crack occurrence No problem Neutralization promotion (mm) KS F 4936 0 0 0 0.08 0.04 salt spray KS D 9502 No problem No problem No problem No problem No problem Chloride ion penetration resistance (mm) KS F 4929 0 0 0 1.5 0.7 My Chemical Resistance_Sulfuric Acid KS M ISO 2812-1 No problem No problem No problem Crack occurrence Swelling My Chemical Resistance_Hydrochloric Acid No problem No problem No problem Crack occurrence Swelling My Chemical Resistance_Sodium Hydroxide No problem No problem No problem Swelling No problem Water resistance KS M ISO 2812-1 No problem No problem No problem No problem No problem Salt water resistance No problem No problem No problem Wrinkle occurrence No problem Oil resistance (gasoline) No problem No problem No problem No problem No problem My contamination resistance Housing Construction Jeon Mun-si-bang-2006 No problem No problem No problem No problem No problem Heat resistance_Soak in boiling water for 8 hours KS F 4936 No problem No problem No problem Wrinkle occurrence Wrinkle occurrence Cold resistance_-50℃7 days No problem No problem No problem Wrinkle occurrence No problem 46 items of drinking water discharge Drinking water quality process test method Not ejected Not ejected Not ejected Not ejected Not ejected Wear resistance (500g, 500 times)
(%) KS F 2813 0.03 0.01 0.01 0.13 0.09 Ozone cracking test KS M ISO 1431-1 No problem No problem No problem Crack occurrence Occurrence of residual cracks

As can be seen in Table 2 above, it was confirmed that the multifunctional organic-inorganic composite waterproofing compositions manufactured according to Examples 1 to 3 of the present invention had significantly superior performance compared to the comparative compositions manufactured according to Comparative Examples 1 and 2.

As described above, those skilled in the art will understand that the present invention can be implemented in other specific forms without changing the technical idea or essential characteristics thereof. Therefore, it should be understood that the embodiments described above are all exemplary and not restrictive. The scope of the present invention should be interpreted that all changes or modifications derived from the meaning and scope of the patent claims described below rather than the detailed description above and the equivalent concepts thereof are included in the scope of the present invention.

Claims (6)

A waterproofing composition containing 10 to 30 wt% of epoxy resin, 20 to 70 wt% of filler, 0.5 to 10 wt% of performance-improving additive, 5 to 20 wt% of reactive diluent, and 8 to 25 wt% of hardener;
The above filler
Containing 100 parts by weight of calcium carbonate, 20 to 50 parts by weight of paramylon-containing fiber, and 1 to 10 parts by weight of cristobalite;
The above performance improving additives
Containing 100 parts by weight of polyoxyethylene polyoxypropylene monobutyl ether, 20 to 50 parts by weight of an epoxy compound of the following chemical formula 1, 1 to 10 parts by weight of a cashew nut shell liquid phenolic resin, and 1 to 10 parts by weight of a boric acid ester compound;
The above hardener
An aromatic amine curing agent alone or a mixture of an aromatic amine curing agent and a thiol curing agent;
The above paramylon-containing fibers
A multifunctional organic-inorganic composite waterproofing composition characterized by containing 85 to 98 wt% of polypropylene resin, 0.1 to 5 wt% of maleic anhydride, and 1 to 10 wt% of paramylon.
[Chemical Formula 1]

(In the equation, n is an integer of 0 or 1)
In the first paragraph,
The above paramylon-containing fibers
It is a paramylon-containing fiber having a resorcinol-formaldehyde-latex layer formed;
The paramylon-containing fiber having the above resorcinol-formaldehyde-latex layer formed
A step of preparing a mixture by mixing 100 parts by weight of paramylon-containing fiber and 1 to 20 parts by weight of avicularin and then drying the mixture.
A step of preparing an immersion product by immersing the above mixture in 90 to 120 parts by weight of a resorcinol-formaldehyde-latex solution, and
It is manufactured by a method including a step of drying the above-mentioned immersion material and then heating it at 80 to 100° C. to manufacture a paramylon-containing fiber having a resorcinol-formaldehyde-latex layer formed thereon;
The above resorcinol-formaldehyde-latex solution
A multifunctional organic-inorganic composite waterproofing composition characterized in that the molar ratio of resorcinol and formaldehyde is 1:1 to 3, and the latex is 10 to 30 parts by weight per 1 part by weight of the total content of resorcinol and formaldehyde.
In the first paragraph,
The above cristobalite
The surface is cristobalite treated with IPL;
A multifunctional organic-inorganic composite waterproofing composition, characterized in that the IPL treatment is performed under conditions in which the voltage is 1000 to 1400 V, the exposure time is 1 to 10 ms, and the frequency is 0.1 to 10 Hz.
In the first paragraph,
The above performance improving additives
A multifunctional organic-inorganic composite waterproofing/protecting agent composition characterized in that it further contains 1 to 10 parts by weight of Cedrol per 100 parts by weight of polyoxyethylene polyoxypropylene monobutyl ether.
In the first paragraph,
The above performance improving additives
Further containing 1 to 10 parts by weight of a methylene malonate compound per 100 parts by weight of polyoxyethylene polyoxypropylene monobutyl ether;
The above methylene malonate compound is
A multifunctional organic-inorganic composite waterproofing/protection material composition characterized by comprising at least one selected from the group consisting of diethyl ethoxymethylene malonate, diethyl aminomethylene malonate, and dimethyl methylene malonate.
A method for constructing a waterproofing method for a concrete structure using a multifunctional organic-inorganic composite waterproofing composition according to any one of claims 1 to 5,
A method for waterproofing a concrete structure, comprising: a step of chipping and cleaning laitance, impurities or deteriorated areas of a concrete structure, and then cleaning the resulting cracks, grooves or deteriorated areas using a fast-hardening putty; a step of applying a modified liquid silicate-based penetrating concrete reinforcing agent to the cleaned surface to form a concrete reinforcing layer; a step of applying a primer to the concrete reinforcing layer to form a primer layer; and a step of applying the multifunctional organic-inorganic composite waterproofing composition to the formed primer layer to form a waterproofing layer.