KR102142100B1 - Environmentally-friendly surface protection layer formation method for enhanced durability, preventing salt damage of steel structure having neutralization, waterproofing, and anticorrosion - Google Patents

Abstract

The present invention relates to an eco-friendly surface protecting method with salt damage and neutralization prevention, and waterproof and anti-corrosive functions of concrete and steel structures and, more specifically, to an eco-friendly surface protecting method, which can have excellent durability of a concrete structure and a steel structure by using a composite elastic polymer material, prevent corrosion caused by external environmental factors, and have excellent waterproof functions.

Description

Environmentally-friendly surface protection layer formation method for enhanced durability, preventing salt damage of steel structure having neutralization, waterproofing, and anticorrosion}

The present invention relates to an eco-friendly surface protection method of preventing damage, neutralization and waterproofing, and anticorrosive functions of concrete and steel structures, and more specifically, using an elastic polymer composite material, excellent durability of concrete structures and steel structures and external environmental factors It is possible to prevent corrosion by, and relates to an eco-friendly surface protection method excellent in waterproof function.

Concrete structures undergo severe physical action, chemical erosion, and physicochemical synergism depending on various weather conditions such as rain, wind, snow, sunlight, etc., and the structure is severely damaged and durability is greatly reduced, and the role of the structure is lost. Accordingly, it is urgent to prepare countermeasures.

In addition, the damage to the environmental conditions in which the steel structure is also severe is more serious. Widely used in bridges, elevated roads, steel structures, etc. in the construction field, iron is a finite earth resource and has a fatal defect of corrosion.

The main factors influencing the corrosion of steel materials are environmental factors, such as sulfur dioxide (SO ₂ ), hydrogen sulfide (H ₂ S), sea salt particles, and temperature and humidity, which are gaseous factors, generally promote corrosion.

As a method of preventing corrosion due to external environmental factors of steel structures, the coating method has been continuously developed and developed, but it is still urgent to develop a technology for a more environmentally friendly coating method because it has not yet reached a satisfactory level.

On the other hand, due to the recent development of construction technology, concrete structures and steel structures are gradually becoming larger and higher. This is evidence of the increasing tendency to emphasize harmony and aesthetics with the surrounding environment along with the function of the structure itself. Such structures are easily contaminated with surfaces due to various external factors, and the appearance may be damaged or damaged. In particular, in urban structures, contamination or damage to the surface frequently occurs due to fine dust in the atmosphere, various organic substances, and acid rain. Due to this, the outer wall of the structure is cleaned using various chemicals or detergents to keep the surface clean and to maintain the urban environment. However, in the conventional cleaning operation, various chemicals or detergents are used, and as the number of times is repeated, there is a problem that the structure surface is damaged. In addition, it has been identified as the main cause of environmental damage, and it is difficult to clean with various effective chemicals or detergents.

Attention has been focused on how to prevent contamination and washable structures to maintain the environmental importance of the above-mentioned structures, and recently, to solve these problems, a coating material having a function of preventing contamination itself has been recently installed on a concrete surface. A method was proposed. Epoxy-based, urethane-based, vinyl-ester-based, fluororesin-based, and acrylic rubber-based materials are used as the coating material.

However, when the epoxy- and urethane-based coating materials are used among the above-described coating materials, their functions do not reach a satisfactory level in order to cope with external conditions such as acid rain, polluted atmosphere, carbon dioxide gas, sulfur dioxide gas, and salt damage. In addition, recently, a metal elastic elastic film adhesion method using an aluminum metal powder and a urethane resin as an adhesive and a coating method using various functions have been tried, but there is much room for improvement as it does not reach a satisfactory level in terms of workability and environment.

In addition, since epoxy, vinyl ester, fluororesin, and acrylic rubber are organic coatings, they have excellent adhesion strength to the initial concrete structure, but the thermal expansion coefficient, deformation characteristics such as drying and shrinkage, show a large difference from concrete, and in the long term At the interface with the concrete structure, the elastic film is detached, and this has the disadvantage that the adhesive strength is lowered. These paints show the property that the adhesion strength with concrete rapidly decreases and the adhesion strength changes rapidly even by the moisture condition of the ground concrete when the surface of the concrete is not completely treated before construction. In addition, since these coating materials are coated in three stages of top, middle, and bottom using paints with different performances during construction, it is not only difficult to construct, but also when defects occur in any one of the three stages of coating, Performance has a great influence, and thus it is difficult to secure long-term durability. In particular, due to the characteristics of general coatings, paints with strong adhesion have relatively low flexibility, and the coatings are easily damaged by micro-cracks naturally occurring in concrete structures, and the durability of the coatings is not integral with the structure behavior against external environmental changes such as weather. This is markedly lowered. On the other hand, flexible paints have good water resistance, but have the disadvantage that they do not fully function due to poor adhesion.

Accordingly, there is a patent for an eco-friendly protection method using an elastic polymer composite material, but since the existing eco-protection method patent performs an elastic coating in two stages, there is a problem in that construction time is increased and labor costs are increased accordingly.

Korean Patent Registration Publication No. 10-0757104 (Announcement date 2007.09.03) Korean Patent Registration Publication No. 10-0454409 (announcement date 2004.10.15)

The present invention primarily improves the composition and composition ratio of the elastic coating agent and the anti-deterioration coating agent used in the surface protection method of KR Patent No. 10-0757104, which is the patent technology of the present applicant, and primarily forms the elastic film forming process that was formed over the second time. It is intended to provide a surface protection method for concrete and steel structures that greatly improves economic efficiency and workability by providing a surface protection method having the same or more effects than the existing surface protection method by the process alone.

In order to solve the above-mentioned problems, the eco-friendly surface protection method of the concrete and steel structure of the present invention includes (a) a surface treatment step for removing latencies and foreign substances on the surface of the concrete structure and the steel structure; (b) a high pressure washing step for removing dust and dirt on the surfaces of concrete structures and steel structures; (c) a base treatment step of applying a putty material on the surface of the resulting product; (d) forming a primer layer with a primer resin containing a ceramic resin on the surfaces of the concrete structure and the steel structure where step (c) is completed; (e) forming an elastic film layer by coating an elastic film forming resin on the primer layer; (f) primary curing step; (g) forming a deterioration prevention film layer by coating a deterioration prevention film resin on the surfaces of the cured concrete structure and the steel structure; And (h) secondary curing.

According to the method of the invention, even if a deterioration film is formed without forming a separate intermediate layer between the elastic film and the deterioration film, there is almost no damage to the elastic film, and the formation of the deterioration film can effectively prevent contamination and block UV. It has excellent light transmittance, environmental and hydrophilicity, excellent decomposition of ozone and various pollutants in the air, excellent stain resistance, excellent transparency of glass, transparent acrylic, and polycarbonate, excellent antibacterial and hydrophilic properties, and has a self-cleaning function. Excellent, life is semi-permanent. In addition, it is possible to perform the elastic film forming process in two steps in the existing surface protection method as a one-step process, and the workability is simple, which greatly reduces the construction cost and construction period.

1 shows a schematic process diagram of an environmentally friendly surface protection method for concrete and steel structures of the present invention.

Looking at the method using the epoxy-based, urethane-based, vinyl-ester-based, fluororesin-based, or acrylic rubber-based coating materials in concrete structures and steel structures according to the prior art, in consideration of the construction method, it takes a long time to construct due to curing time and the process itself As well as being complicated, it is necessary to improve problems such as construction errors in the construction process due to the use of unnecessary materials. In addition, considering the method using an epoxy-based, urethane-based, vinyl-ester-based, fluororesin-based, or acrylic rubber-based coating material in the concrete structure and the steel structure according to the prior art from an economical point of view, the complex process is simplified to increase the convenience of construction and Therefore, it is required to reduce the overall cost by simplifying the process so as to reduce the occurrence of construction errors due to the increase in the number of processes and reducing the use of unnecessary materials and shortening the construction period. Also, when looking at the existing construction method from the environmental point of view, the construction method of the concept of the object (target structure) is mainstream rather than the construction method of the user (user citizen and surrounding environment). The results are somewhat inadequate in terms of harmony with the surrounding environment and use of the citizen, while being inclined to its effectiveness and performance. For example, it has the disgrace that it is a major cause of air pollution due to the generation of volatile organic compounds (VOC) generated in the process of paint painting. In particular, in the process of use in paint, 40% of the total VOC in Korea is discharged, and its contribution rate is very high. Also, the discharged VOC is harmful to health, such as irritating the respiratory system and causing disorders in the nervous system. The government's and companies' efforts to reduce the situation are more urgent. Particularly, companies to achieve the goals set out in the agreement, such as allowing companies and governments to develop and promote various programs to economize the demand pattern of the domestic paint market, and to promote policies to expand the low VOC paint market- In a situation that emphasizes the government's partnership, the development of an eco-friendly coating method without VOC is urgently needed. In addition, even if the performance of the structure is improved by applying the coating method, as a result, it cannot be said that the purpose of the coating (coating) was achieved if the citizens of the use did not achieve a pleasant urban environment. In addition, it is necessary to actively introduce a maintenance concept (contamination prevention and ease of cleaning) that can continuously maintain the purpose of the coating (coating).

The inventor's existing patented technology (Korea Patent Registration Publication No. 10-0757104), an environmentally friendly surface protection method for concrete and steel structures, uses the pH of the composition for forming a deterioration prevention film in the range of 7 to 10 in view of the above points to prevent the deterioration prevention film. In the case of forming, unlike the conventional case, since the film formed under the deterioration preventing film is not damaged, it is not necessary to form a separate intermediate layer between the elastic film (middle coating) and the deterioration preventing film (top coating). Therefore, unlike conventional cases, the workability is improved, and the construction cost can be reduced compared to the existing method through a method that lowers the water content without impairing the paint safety and pigment dispersibility, so that it can be quickly cured in a short period of time when applied to various structures. And it provided a surface protection method for increasing the durability and anticorrosion of concrete structures and steel structures, which can achieve the effect of reducing the construction period, and waterproofing. In addition, when forming a protective elastic film, it is possible to form a concrete structure and a steel structure that are harmless to the environment and the human body by using eco-friendly materials, and excellent mechanical performance has greatly increased durability such as neutralization, salt damage, waterproofing, and corrosion protection of the structure.

The eco-friendly surface protection method of the existing concrete and steel structures according to the patent technology of the present inventor performed the formation of an elastic film, which is a middle coat, through a two-step process. In addition to the corresponding primer resin, if the composition and composition ratio of the elastic film forming resin and the deterioration preventing film resin are partially modified and improved, the elastic film forming process is performed in one step, while the partial protection effect of the existing patented technology is found. It has been found that it can be (see Figure 1 schematic process diagram).

Hereinafter, the eco-friendly surface protection method of the concrete and steel structures of the present invention will be described in more detail.

The environmentally friendly surface protection method of the concrete and steel structure of the present invention includes (a) a surface treatment step for removing latencies and foreign substances on the surface of the concrete structure and the steel structure; (b) a high pressure washing step for removing dust and dirt on the surfaces of concrete structures and steel structures; (c) a base treatment step of applying a putty material on the surface of the resulting product; (d) forming a primer layer with a primer resin containing a ceramic resin on the surfaces of the concrete structure and the steel structure where step (c) is completed; (e) forming an elastic film layer by coating an elastic film forming resin on the primer layer; (f) primary curing step; (g) forming a deterioration prevention film layer by coating a deterioration prevention film resin on the surfaces of the cured concrete structure and the steel structure; And (h) secondary curing.

Step (a) is a surface treatment process for first removing the lattice and foreign substances on the surface of the concrete structure and the steel structure, and the surface treatment step is for removing the lattice and foreign substances on the surface of the structure, such as conventional sandpaper polishing or grinding. The same various surface treatment methods can be employed. In the present invention, it is preferable to perform wet air grinding in particular when removing the latency, because it is possible to prevent complaints and atmospheric environment problems due to dust generation during the grinder operation.

After the surface treatment step is completed, step (b), which is a high-pressure washing step for removing dust and dust on the surface of the structure, is performed using a high-pressure sprinkler. When using such a high-pressure washing machine, a pressure range is preferably 200 to 300 bar.

After the high pressure washing, step (c), which is a base treatment process for forming a base by performing an elastic putty process for applying an elastic putty material, is performed. The elastic putty has the advantage of being able to heal reticular cracks or micro cracks and respond to initial cracks by using an elastic putty, that is, a repair agent, when micro cracks occur due to shrinkage expansion of concrete and steel structures.

Next, the step (d) of forming a primer layer is performed, and the primer layer has excellent adhesion regardless of the material of the structure, and condensation, humidity, water vapor, etc. generated in the natural environment (when repeating high and cold cycles) Silver is released through a hole having a porous structure of 0.0004 µm, and fog and rainwater having a size of 1.00 to 6.000 µm block penetration and have a function of protecting the base material, thereby extending the durability of the deterioration and neutralization process. In particular, it prevents intrusion into various harmful substances and gases in the atmosphere, and is provided with excellent functions such as acid resistance, alkali resistance, salt water resistance, and heat resistance.

The primer resin used for forming the primer layer in step (d) can be used alone as the ceramic resin disclosed in Korean Patent Registration No. 10-0757104, but preferably styrene for improving adhesion and chemical resistance to the elastic coating layer. -15 to 25% by weight of an alkyl acrylate copolymer resin, 35 to 50% by weight of a ceramic resin and a resin containing a residual amount of water can be used, more preferably 18 to 23% by weight of a styrene-alkyl acrylate copolymer resin , Ceramic resin may be used a primer resin containing 37 to 45% by weight and the residual amount of water. At this time, if the content of the styrene-alkyl acrylate copolymer resin is less than 15% by weight, there may be a problem that the adhesion between the primer and the medium is insufficient, and the excess of 25% by weight is excessively used and the content of the ceramic resin is relatively small. As the effect of improving the chemical resistance decreases, and there is no further increase in the adhesion with the middle, it is uneconomical.

Further, the ceramic resin may include a polymer obtained by polymerizing a mixture of 100 parts by weight of silicon tetraalkoxide, 30 to 45 parts by weight of methyl methacrylate, and 120 to 180 parts by weight of water.

Next, step (e) is a step of forming an elastic coating layer, and an elastic coating layer is coated on the primer layer to form an elastic coating layer.

As described above, conventionally, a primary elastic film is formed by coating and drying a composition for forming a primary elastic film comprising an organic-inorganic composite resin and a phase transition functional material, and then an organic-inorganic composite resin on top of the primary elastic film , A secondary elastic film was formed by painting and drying the composition for forming a secondary elastic film comprising a phase change functional material and a purification functional composite material. On the other hand, the present invention can form an elastic film in a one-step process rather than two steps by using a novel elastic film-forming resin having a different composition and composition ratio from the previous one.

The elastic film-forming resin used in the present invention includes an organic-inorganic composite resin, a water-soluble latex, a phase transition functional material, a purifying functional composite material, nylon fibers, a shrinkage reducing agent, and an organic solvent.

The organic-inorganic composite resin in the elastic film-forming resin component comprises 35 to 45% by weight, preferably 35 to 42% by weight, and more preferably 38 to 42% by weight of the total weight of the elastic film-forming resin.

In addition, the organic-inorganic composite resin is a ceramic resin 20 to 25% by weight, urethane-(meth)acrylate-silane copolymer resin 40 to 50% by weight, acrylic emulsion resin 10 to 20% by weight and residual organic solvent is mixed It may be prepared, preferably 22 to 25% by weight of a ceramic resin, 40 to 45% by weight of a urethane-(meth)acrylate-silane copolymer resin represented by the following formula 1, acrylic emulsion resin represented by the following formula 2 It may be prepared by mixing 12 to 16% by weight and the remaining amount of the organic solvent.

Among the organic/inorganic composite resin components, the ceramic resin may be a polymer obtained by polymerizing a mixture of 100 parts by weight of silicon tetraalkoxide, 400 to 550 parts by weight of methyl methacrylate, and 120 to 180 parts by weight of water, preferably silicone It may be a polymer obtained by polymerizing a mixture of 100 parts by weight of tetraalkoxide, 420 to 500 parts by weight of methyl methacrylate, and 140 to 170 parts by weight of water.

Among the organic-inorganic composite resin component, the urethane-(meth)acrylate-silane copolymer resin may be a urethane-(meth)acrylate-silane copolymer resin represented by the following Chemical Formula 1.

[Formula 1]

이고, 바람직하게는 R²는 메틸기, 에틸기, 이소프로필기 또는

이며, 더욱 바람직하게는 이소프로필기 또는

이다. 그리고, 화학식 1의 상기 R³은 -OCH₃, -OCH₂CH₃, -OCH₂CH₂CH₃ 또는 -OCH₂CH₂CH₂CH₃이며, 바람직하게는 -OCH₃, -OCH₂CH₃ 또는 -OCH₂CH₂CH₃이며, 더욱 바람직하게는 -OCH₂CH₃이다.In Formula 1, R ¹ is a hydrogen atom, a C ₁ ~ C ₃ linear alkyl group or a C ₃ ~ C ₅ pulverized alkyl group, preferably R ¹ is a hydrogen atom, a methyl group, an ethyl group or an isopropyl group . And, R ² of Formula 1 is a hydrogen atom, C ₁ ~ C ₃ straight-chain alkyl group, C ₃ ~ C ₅ pulverized alkyl group or

And preferably, R ² is a methyl group, ethyl group, isopropyl group, or

Is, more preferably isopropyl group or

to be. In addition, R ³ in Formula 1 is -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ or -OCH ₂ CH ₂ CH ₂ CH ₃ , preferably -OCH ₃ , -OCH ₂ CH ₃ Or -OCH ₂ CH ₂ CH ₃ , and more preferably -OCH ₂ CH ₃ .

Among the organic-inorganic composite resin component, the acrylic emulsion resin may include an acrylic copolymer represented by the following Chemical Formula 2.

[Formula 2]

In Chemical Formula 2, R ¹ is a hydrogen atom or a C ₁ to C ₃ straight-chain alkyl group, preferably a hydrogen atom or a methyl group. In addition, each of R ² and R ³ in Chemical Formula 2 is independently a hydrogen atom or a C ₁ to C ₅ straight-chain alkyl group, and preferably a methyl group or an ethyl group. Further, R ⁴ in Formula 2 is an acetyl group or a diacetyl group, and preferably an acetyl group. In addition, each of a, b, c and d is an integer of 1 to 50 independently, and preferably each of a, b, c and d is an integer of 5 to 20 independently.

The organic solvent in the organic-inorganic composite resin component may be one or more selected from methanol, ethanol, isopropyl alcohol, isobutanol, methyl acetate, ethyl acetate, butyl acetate, acetone and methyl isobutyl ketone, and more preferably Can be used by mixing one or more selected from methanol, ethanol, ethyl acetate and methyl isobutyl ketone.

The water-soluble latex among the elastic film-forming resin components is used to improve elasticity, and is used in an amount of 2 to 5% by weight, preferably 3 to 4.5% by weight, of the total weight of the elastic film-forming resin. In addition, the water-soluble latex includes 55 to 60% by weight of the synthetic latex solids and the remaining amount of water, preferably 57 to 60% by weight of the synthetic latex solids and the remaining amount of water.

Among the elastic film-forming resin components, the phase change functional material also has a phase change heat storage, PEG (polyethylene glycol), linear chain alkanes (C _n H _2n+2 ), octatecane, C ₁₈ H ₂₈ ), heptadecane (C ₁₇ H ₃₆ ), ZrC, microcapsules containing a phase change material, and the like can be used. These materials are absorbed and stored at 3 to 12°C at 25 to 35°C, and then radiated when the ambient temperature is below 22 to 23°C to protect the base material and release stored heat at subzero temperatures. The content of the phase change functional material is preferably 2 to 5% by weight, preferably 3.5 to 5% by weight, of the total weight of the elastic film-forming resin. If the content of the phase change functional material is less than 2% by weight, heat is blocked at the required temperature of 22°C. If the function is high and exceeds 5% by weight, it is not preferable because the required temperature is lower than 22°C.

Among the elastic film-forming resin components, the purifying functional composite material has a purifying function with complex functions such as precious stones, germanium, and antibacterial ceramics having a self-cleaning function in various contaminated environments (air, underwater deposition, rain, fog, etc.) Contains substances. The purification functional composite content is preferably 4 to 7% by weight, preferably 5 to 6.5% by weight of the total weight of the elastic film-forming resin.

In addition, the nylon fiber is a reinforcing fiber, and serves to improve the mechanical strength of the elastic coating layer and prevent cracking. It is recommended to use such a nylon fiber having a fiber length of 5 to 10 mm, and if the fiber length of the nylon fiber is less than 5 mm, the length may be too short to improve mechanical strength. If the fiber length exceeds 10 mm, it is rather too long. There may be a problem that the nylon fibers are not bundled and evenly dispersed in the elastic film forming resin. And, the content of the nylon fiber is preferably 1 to 2% by weight, preferably 1.2 to 1.8% by weight of the total weight of the elastic film-forming resin.

The shrinkage reducing agent serves to prevent the elastic coating layer from rapidly contracting when the coated elastic film forming resin is cured, and the shrinkage reducing agent includes a polyoxyalkylene compound, preferably polyoxy (C ₃ ~ C ₅ alkylene) can be used. In addition, the content of the shrinkage reducing agent is preferably 0.01 to 0.2% by weight, preferably 0.05 to 0.15% by weight of the total weight of the elastic film-forming resin.

The organic solvent in the elastic film-forming resin component, the organic-inorganic composite resin is well dissolved in the elastic film-forming resin component, water-soluble latex, phase transition functional materials, purification functional composites, etc. can be used well mixed, preferably methanol , Ethanol, isopropyl alcohol, isobutanol, methyl acetate, ethyl acetate, butyl acetate, acetone and methyl isobutyl ketone may be used, and more preferably, methanol, ethanol, ethyl acetate and methyl isobutyl ketone may be used. It may be used by mixing one or more selected from.

The elastic film-forming resin may further include additives such as fillers, antibacterial agents, pigments, and walnut shell powders, in addition to the above-described components. Among the additives, titanium oxide (TiO 2 ), barium-based filler, zirconium-based filler, illite filler, or a mixture thereof may be used as the filler, and impact strength and durability may be increased by adding the filler. Among the additives, the antibacterial agent is intended to prevent oxidation and aging of the concrete structure and the steel structure as various microorganisms, bacteria, and fungi grow naturally due to moisture inside the interface between the concrete structure and the steel structure. Antibacterial agents extracted from can be used. Among the additives, the pigment serves to prevent yellowing and aging by ultraviolet rays, and various types of inorganic pigments may be used, for example, TiO ₂ and Cr ₂ O ₃ pigments. Among the additives, walnut shell powder increases the impact resistance and hardness of the surface of concrete structures and steel structures, and forms an elastic film with embossing to improve the aesthetics of the surfaces of concrete structures and steel structures, and has a particle size of 400 mesh or more. You can use

The elastic coating layer of step (e) is preferably formed to a thickness of 160 to 220 μm, preferably 170 to 200 μm, depending on the situation, and finished with coating in the same way, emphasizing aesthetics outside the structure and requiring cleanliness. This part can be used for piers, bridge railings, iron structure railings, sidewalk overpasses, etc. by applying a pollution prevention coating. The elastic coating layer combines excellent adhesion and ductile polymer binders to improve elongation to impart crack follow-up performance, thereby securing microcracks naturally occurring in the structure and adaptability to concrete deformation and chloride ion, which is the cause of rebar corrosion , It can secure the resistance to chemical infiltration of carbon dioxide, moisture, etc., and improve the durability through the aesthetic improvement of the structure and the suppression of organic substances by preventing contamination.

Next, step (f) is a primary curing step, and the elastic coating layer is for minimizing harmful effects such as temperature, load, impact, or damage, and curing conditions include a temperature of 15°C to 25°C and 50% ~ It is preferably performed for 1 to 2 days under 70% relative humidity.

Next, step (g) is a step of forming a deterioration film layer by coating a deterioration film resin on the surfaces of the cured concrete structure and the steel structure.

The deterioration-prevention film resin includes an organic-inorganic composite resin, liquid anhydrous sodium silicate, a full-wavelength region-type radiation material, a far-infrared wavelength region-type radiation material, and an organic solvent, preferably 50 to 60 wt% organic-inorganic composite resin, liquid anhydrous Sodium silicate 5 to 10% by weight, 5 to 10% by weight of the full-wavelength radiation material, 10 to 15% by weight of the far-infrared wavelength range radiation material and the remaining amount of organic solvent, more preferably organic-inorganic composite resin 52 to 58% by weight %, 5 to 7% by weight of sodium anhydrous sodium anhydride, 6.5 to 9.0% by weight of a full-wavelength region type radiation material, 10 to 13.5% by weight of a far-infrared wavelength range type radiation material, and a residual amount of an organic solvent.

The organic-inorganic composite resin used for the deterioration prevention film resin is the same as the organic-inorganic composite resin used for the elastic film-forming resin component.

Among the deterioration preventing film resin components, the liquid anhydrous sodium silicate serves to strengthen the waterproofing and antifouling function of the deterioration preventing film, and the liquid anhydrous sodium silicate includes 70 to 90% by weight of sodium meta anhydride. In addition, the meta-anhydrous sodium silicate contains silicic acid and carbonate in a weight ratio of 65 to 68:32 to 35. The liquid anhydrous sodium silicate is a meta-anhydrous sodium silicate having a very high content, the first step of preparing a mixture and a mineral mineral mixture of silica and sodium carbonate; Step 2 to obtain a melt by melting the mixture; Cooling the melt to obtain crystals, and then crushing the crystals to prepare a crushed product; And after adding the mixed solution of the pulverized material and water to the melting furnace, it may be prepared by performing a process comprising four steps of dissolving and cooling the pulverized material.

When preparing liquid anhydrous sodium silicate, in the first step, the mixture is composed of silica and sodium carbonate in a weight ratio of 1: 1.30 to 1.55, preferably silica and sodium carbonate in a weight ratio of 1: 1.40 to 1.50, and more preferably 1: 1.40 to 1.45. It can be included in a weight ratio.

In the production of liquid anhydrous sodium silicate, in step 2, the molten silver is mixed with minerals into a hopper, and then fed into an electric furnace using a feeder, followed by heat of 1,800°C or higher, preferably 1,800°C Melting may be performed by applying heat of ˜1,880° C., more preferably 1,800° C. to 1,850° C.

In the production of liquid anhydrous sodium silicate, step 4 is a process of dissolving the pulverized material in a mixed solution of pulverized crushed crystals and water in step 3, with respect to 100 parts by weight of water, the pulverized product 20 to 30 To be added, it is preferable to mix the water and the pulverized material so that the pulverized product is 20 to 25 parts by weight based on 100 parts by weight of water. And, the dissolution of the fourth step can be performed for 3 hours to 5 hours under 170°C to 190°C and 1.5 to 3.2 kgf/cm ² , preferably 3 under 175°C to 185°C and 1.7 to 2.8 kgf/cm ² It can be performed for an hour to 5 hours.

Among the deterioration preventing film resin components, the full-wavelength region type radiation material may include one or more selected from manganese dioxide (MnO ₂ ), chromium oxide, iron oxide, and cobalt oxide (CoO).

In addition, the far-infrared wavelength region type radiation material among the deterioration prevention film resin components may include at least one selected from zirconia (ZrO ₂ ), alumina, zircon (ZrO ₂ , SiO ₂ ), and titanium dioxide (TiO ₂ ).

When titanium dioxide is used as a far-infrared wavelength region type radiation material, titanium dioxide is a titanium raw material; One or more solvents selected from distilled water and organic solvents; Patriotism; And Fe, Al, Si, Cu, Ni, Ge, Ba, Mn, Mg, Ag, Au, Cr, and Zn; one or more metals; after hydrolysis and peptization reaction in a hydrothermal synthesizer, the composition The content of titanium dioxide is adjusted to 3 to 30% by weight to form titanium dioxide sol (TiO ₂ Sol), and the pH of the sol solution can be adjusted to 7 to 10 to prepare. The titanium dioxide sol is highly active and has excellent storage stability, and can be stored for more than 6 months. As the titanium raw material, one or more selected from titanium alkoxide, titanium chlorite, titanium narrate, titanium schlade, and titanium aminooxalate may be used. And, as the peptizing agent, one or more selected from trimethylamine, dimethylamine, methylamine, ethylamine, diethylamine and triethylamine may be used.

The hydrothermal reaction in the hydrothermal synthesizer is a reaction to crystallize amorphous at high temperature and high pressure, and it is preferable that the reaction time is 100 to 250°C, 5 to 20 atmospheres, and the reaction time ranges from 2 to 10 hours. And, the content of metal in the titanium dioxide sol is 0.1 to 5 parts by weight based on 100 parts by weight of titanium dioxide, the mixing molar ratio of titanium dioxide and water in the titanium dioxide sol is 1:50 to 1:200, and the titanium dioxide It is preferable that the mixed molar ratio of titanium dioxide and a peptizing agent in the sol is 1:0.1 to 1:3.

Titanium dioxide has uniform titanium particle dispersibility, excellent storage stability, and has a sol pH of 7 to 10 as neutral or weak alkali, even if it is applied directly to the top of the elastic film, there is no damage, so no coating is necessary. . In addition, when titanium dioxide is used as a far-infrared wavelength region type radiation material constituting the deterioration preventing film, Fe, Al, Si, Cu, Ni, Ge, Ba, Mn, Mg, and the like described above on the titanium dioxide surface according to the above-described manufacturing process. When a coating film made of at least one metal among Ag, Au, Cr, and Zn is formed to form an anti-deterioration film using these materials, unlike the conventional case, the elastic coating layer or the like under the anti-deterioration film is not damaged. If the pH of the titanium oxide is less than 7 (alkaline), the surface of the coated object is damaged, and if it exceeds 10, it is not preferable because the titanium dioxide becomes acidic and the underlying film is damaged when forming the film using it.

Among the deterioration prevention film resin components, one or more selected from methanol, ethanol, isopropyl alcohol, isobutanol, methyl acetate, ethyl acetate, butyl acetate, acetone, and methyl isobutyl ketone may be used, and more preferably One or more selected from methanol, ethanol, ethyl acetate and methyl isobutyl ketone can be used in combination.

After the deterioration preventing film is formed in step (g) as described above, secondary curing is performed. The curing conditions of the secondary curing process are preferably performed for 5 to 7 days under a temperature of 15°C to 25°C and a relative humidity of 50% to 70%.

According to the method of the present invention, without forming a separate intermediate layer between the elastic film and the anti-deterioration film, an anti-deterioration film can be formed to effectively prevent contamination and UV, and thus has excellent light transmittance, environmental and hydrophilic properties, and ozone, various in the atmosphere. Excellent pollutant decomposition function, excellent stain resistance, excellent transparency of glass, transparent acrylic, and polycarbonate, excellent antimicrobial and hydrophilic properties, and excellent self-cleaning function. Air can be significantly reduced.

The surface of the material is generally hydrophobic due to the presence of organic matter. Therefore, since detergent is not used to remove organic substances when washing, there is a tendency that the washing is poor. However, the deterioration preventing film formed by the method of the present invention has hydrophilicity because organic substances contaminated on the surface are decomposed and removed when exposed to ultraviolet rays. It has a high self-cleaning ability, blocks UV rays and does not deform. Therefore, according to the method of the present invention, the maintenance cycle of the structure is extended, and it has an eco-friendly function to prevent the accumulation of contaminants on the surface of the structure, and the construction period is very shortened.

The application method of the present invention is not particularly limited in its application field, such as sewage culverts, electric power zones, communication zones, common wards, underground structures such as subways, water purification plants, sewage treatment plants, swimming pools, water facilities, waterway culverts/removals Used for general structures such as hydraulic structures, tunnels, bridges, sidewalk viaducts, underground roadways, retaining walls, and building structures, dams, pier facilities, breakwaters, offshore steel pipes, LNG tanks/oil tanks, and special structures such as industrial plant facilities.

Hereinafter, the present invention will be described in more detail through examples, but the following examples are not intended to limit the scope of the present invention, which should be interpreted to help understand the present invention.

Example

Preparation Example 1: Preparation of the specimen

A 10×10×40 cm prismatic specimen was used as a standard, and the number of specimens was two or more for the same test. The specimens were produced in accordance with KS F2403 (Method of manufacturing and curing specimens for compressive and flexural strength measurements in the laboratory).The compaction of concrete is made of concrete compaction rods (16 mm in diameter and 50 cm in length) or an internal vibrator (roof) In case of compaction rod, 26 times for each floor, and internal vibrator was compacted at a rate of once per 100 cm ² .

After the compaction, the specimen was placed in a horizontal place until the concrete hardened, and the surface portion was covered with plate glass, steel plate, and wet cloth to prevent water vapor evaporation of the specimen, and demoulding of the mold was carried out when the concrete was cured, The demolding time was 24 hours or more and 48 hours or less after the injection was finished, and a specimen was produced.

Preparation Example 2: Preparation of primer resin

(1) Ceramic resin

The polymer obtained by polymerizing a mixture of 100 parts by weight of silicon tetraalkoxide, 37 parts by weight of methyl methacrylate and 140 parts by weight of water was prepared as a ceramic resin.

(2) Primer resin

Primer resin was prepared by mixing 22.3% by weight of styrene-ethyl acrylate copolymer resin, 40.5% by weight of the ceramic resin, and the remaining amount of water.

Preparation Example 3-1: Preparation of an elastic film-forming resin

(1) Ceramic resin production

The polymer obtained by polymerizing a mixture of 100 parts by weight of silicon tetraalkoxide, 450 parts by weight of methyl methacrylate and 165 parts by weight of water was prepared as a ceramic resin.

(2) Preparation of urethane-(meth)acrylate-silane copolymer resin

40.19 g (0.1625 mol) of 3-triethoxysilylpropyl isocyanate is 34.81 g (0.1625 mol, 214.22 MW) of 3-acryloxy-2-hydroxy-propyl methacryl in the presence of 1000 ppm of DBTDL for about 24 hours. After reacting with rate (AHPM), 1.6 g (0.0075 mol) of additional AHPM was added and further reacted for about 24 hours to obtain the product as an opaque white oil.

[Formula 1-1]

이며, R³은 - OCH₂CH₃이다.In Formula 1-1, R ¹ is a methyl group, and R ² is

And R ³ is —OCH ₂ CH ₃ .

(3) Manufacturing organic/inorganic composite resin

23.5% by weight of the ceramic resin, 42% by weight of the urethane-(meth)acrylate-silane copolymer resin, 13.8% by weight of an acrylic emulsion resin represented by the following Chemical Formula 2-1, and residual organic solvents (ethyl acetate and methyl isobutyl) Ketone 1: 0.5 weight ratio) was mixed to prepare an organic-inorganic composite resin.

[Formula 2-1]

In Formula 2-1, R ¹ is a methyl group, R ² and R ³ are methyl groups, R ⁴ is an acetyl group, and a, b, c and d are each independently an integer of 7 to 15.

(4) Preparation of water-soluble latex

A water-soluble latex containing 58.4% by weight of synthetic latex solids and a residual amount of water was prepared.

*(5) Preparation of phase transition functional substances

PEG and octatecan were mixed at a weight ratio of 1: 2.5 to prepare a phase transition functional material.

(6) Preparation of elastic film-forming resin

The organic-inorganic composite resin 39.7% by weight, the water-soluble latex 3.4% by weight, the phase transition functional material 4.2% by weight, yangyangseok 5.7% by weight, a functional composite of purification, 1.4% by weight of nylon fiber 5 ~ 10 mm fiber, shrinkage reducing agent An elastic film-forming resin was prepared by mixing 0.1% by weight of polyoxypropylene and the remaining amount of organic solvent (ethanol, ethyl acetate and methyl isobutyl ketone = 1: 4: 0.5 weight ratio).

Preparation Example 3-2: Preparation of elastic film-forming resin

Using the same organic-inorganic composite resin, water-soluble latex, phase transition functional substance, purification functional composite, nylon fiber, shrinkage reducing agent and organic solvent as in Preparation Example 3-1, 41.7 wt% organic-inorganic composite resin, 3.1 wt% water-soluble latex , Phase change functional material 3.7 wt%, purifying functional composite 6.4 wt%, nylon fiber 1.8 wt%, shrinkage reducing agent 0.1 wt% and the balance of the organic solvent was mixed to prepare an elastic film forming resin.

Preparation Example 4: Deterioration prevention film resin production

(1) Organic and inorganic composite resin

As the organic-inorganic composite resin, the same organic-inorganic composite resin used in the elastic film-forming resin of Preparation Example 3 was prepared.

(2) Liquid anhydrous sodium silicate

Silica and sodium carbonate were mixed at a weight ratio of 1:1.42 to put the mixture in a hopper, and the mixture was melted by putting it in an electric furnace using a feeder. At this time, the melting temperature was about 1800 ~ 1810 ℃. After cooling the melt to obtain a crystal, it was pulverized to obtain a pulverized product. Next, with respect to 100 parts by weight of water, 22 parts by weight of the pulverized material was mixed to prepare a mixture, and then it was introduced into a melting furnace. Then, after the melting furnace was brought to a temperature of 180 to 185°C and a pressure of 1.80 to 1.90 kgf/cm ² , the pulverized material was dissolved in water for 5 hours to obtain a liquid sodium anhydrous sodium silicate.

The liquid anhydrous silicate contained 84% by weight of meta anhydrous sodium silicate, the remaining amount of water, and essential impurities. And, the meta anhydrous sodium silicate contains silicic acid and carbonate in a weight ratio of about 67:33.

(3) Preparation of far-infrared wavelength region type radiation material

After the composition containing titanium tetraethoxide, distilled water, peptide triethylamine, and metal is subjected to hydrolysis and peptization reaction in a hydrothermal synthesizer, the content of titanium dioxide in the composition is adjusted to about 20% by weight of titanium dioxide sol (TiO ₂ Sol) was formed, and the pH of the sol solution was adjusted to about 8 to prepare a far-infrared wavelength region type radiation material.

(4) Deterioration prevention film resin production

55% by weight of the organic-inorganic composite resin, 5% by weight of the liquid anhydrous sodium silicate, 6.9% by weight of zirconia as a full-wavelength radiation material, 11.3% by weight of the far-infrared wavelength-area radiation material and the remaining amount of organic solvent (ethanol, acetic acid) Deterioration preventing film resin was prepared by mixing ethyl and methyl isobutyl ketone = 1: 4.5: 1 weight ratio).

Example 1: Application of surface protection method

Latency and foreign matter on the surface of the specimen of Preparation Example 1 were removed, and a high pressure washing step was performed. Then, after drying, the primer resin prepared in Preparation Example 2 was applied to the dried specimen to form a primer layer.

Next, after coating the elastic film-forming resin prepared in Preparation Example 3-1 on the top of the primer layer to form an elastic film layer (thickness of about 188 ~ 190㎛), for 1 hour under a relative humidity of 20 ℃, 70% for 1 hour Tea curing was conducted.

Next, after forming the deterioration prevention film layer by coating the deterioration prevention film resin prepared in Preparation Example 4 on the cured elastic coating layer, the second curing was performed for 5 days at 20°C and 70% relative humidity, and the surface protection method was applied. A primer layer-elastic coating layer-deterioration prevention film layer was sequentially formed over the specimen.

Example 2

The same procedure as in Example 1 was performed, but when forming the elastic coating layer, the elastic coating forming resin of Preparation Example 3-2 was used instead of the elastic coating forming resin of Preparation Example 3-1.

Comparative Example 1

By performing the surface protection method on the specimen of Preparation Example 1 in the same manner as the method disclosed in Korean Patent Registration Publication No. 10-0757104, the primer layer-primary elastic coating layer-2 secondary elastic coating layer-deterioration prevention film layer was sequentially on the specimen. As it was.

Specifically, the ceramic resin of Preparation Example 2 was used alone as the primer resin, and the resin for forming the primary elastic coating layer was composed of 12.5 parts by weight of ceramic resin, 12.5 parts by weight of acrylic resin, 25 parts by weight of urethane resin, and 7 parts by weight of phase change material. The secondary elastic film layer-forming resin was composed of 12.5 parts by weight of a ceramic resin, 12.5 parts by weight of an acrylic resin, 25 parts by weight of a urethane resin, 6.5 parts by weight as a phase change material, and 7 parts by weight of precious stones as a purification functional composite material. . In addition, the composition for forming the deterioration prevention film is an organic-inorganic composite resin, 13 parts by weight of a ceramic resin, 12 parts by weight of an acrylic resin, 25 parts by weight of a urethane resin, 7 parts by weight of manganese dioxide, which is a full-wavelength range type radiation material, and a far-infrared wavelength range type radiation material. What was prepared by mixing 6 parts by weight of titanium oxide sol was used.

Comparative Example 2

The same procedure as in Example 1 was carried out, but as the primer resin, the ceramic resin of Preparation Example 2 was used alone.

Experimental Example: Measurement of physical properties

The physical properties of the specimens subjected to the surface protection method of Example 1 and Comparative Examples 1 to 2 were measured, and the results are shown in Table 2, and the measurement methods are shown in Table 1 below.

Test Items Test Methods Promotion of neutralization KS F 4986 Salt spray
200 hours KS D 9502 Accelerated weathering (300 hours) KS M 5000 UV protection rate JISA 5759 46 items of drinking water dissolution Drinking Water Quality Process Test Method
(Ministry of Environment Notice 2004-188) Bond strength
(N/mm ² ) After standard curing KS F 4986 After accelerated weathering After repeated cooling and heating After alkali resistance After salt water resistance Film formation
Appearance After standard curing KS F 4986 After accelerated weathering After repeated cooling and heating After alkali resistance After salt water resistance Chemical resistance (sulfuric acid, hydrochloric acid, sodium hydroxide) KS M ISO2812 Flex resistance KS M 5000 Water permeability KS F 4986 Impact resistance KS D 6711 Pollution resistance Housing Construction Specifications Whitening resistance KS M 5000M Chloride ion penetration resistance KS F 4986 Moisture permeability KS F 4986 VAC ASTM D 3257 VOC KS M ISO 11880 Whether lead, cadmium, hexavalent chromium or mercury are detected KS M ISO 3856

Test Items Example 1 Example 2 Comparative Example 1 Comparative Example 2 Promotion of neutralization 0 mm 0 mm 0 mm 0 mm Salt spray
200 hours nothing strange nothing strange nothing strange nothing strange Accelerated weathering (300 hours) nothing strange nothing strange nothing strange nothing strange UV protection rate 99.656% 99.656% 99.795% 99.674% 46 items of drinking water dissolution Not detected Not detected Not detected Not detected Bond strength
(N/mm ² ) After standard curing 4.5 5.7 1.9 1.3 After accelerated weathering 29 31 17 14 After repeated cooling and heating 26 28 15 14 After alkali resistance 22 25 16 17 After salt water resistance 23 25 15 12 Film formation
Appearance After standard curing nothing strange nothing strange nothing strange nothing strange After accelerated weathering nothing strange nothing strange nothing strange nothing strange After repeated cooling and heating nothing strange nothing strange nothing strange nothing strange After alkali resistance nothing strange nothing strange nothing strange nothing strange After salt water resistance nothing strange nothing strange nothing strange nothing strange Chemical resistance (sulfuric acid, hydrochloric acid, sodium hydroxide) nothing strange nothing strange nothing strange nothing strange Flex resistance nothing strange nothing strange nothing strange nothing strange Water permeability Not pitched Not pitched Not pitched Not pitched Impact resistance nothing strange nothing strange nothing strange nothing strange Pollution resistance nothing strange nothing strange nothing strange nothing strange Whitening resistance nothing strange nothing strange nothing strange nothing strange Chloride ion penetration resistance 135 131 120 102 Moisture permeability 1.1 1.2 1.3 1.1 VAC 0.02 0.03 0.04 0.02 VOC 185 193 231 187 Whether lead, cadmium, hexavalent chromium or mercury are detected Not detected Not detected Not detected Not detected

Looking at the experimental results in Table 1, when compared with Comparative Example 1 in which the primary and secondary elastic coating layer formation process was performed, when comparing Examples 1 to 2 with the formation of one elastic coating layer with Comparative Example 1, most The physical properties correspond almost, and the chloride ion penetration resistance showed better results than Comparative Example 1, and particularly, the adhesion strength was relatively excellent. And, in the case of Comparative Example 2, when compared with Example 1, there was a problem that the adhesion strength was significantly reduced, but rather, the result was worse than that of Comparative Example 1.

Claims (5)

(A) a surface treatment step for removing the lattice and foreign matter on the surface of the steel structure;
(b) high pressure washing step to remove dust and dirt from the surface of the steel structure;
(c) a base treatment step of applying a putty material on the surface of the resulting product;
(d) forming a primer layer with a primer resin containing a ceramic resin on the surface of the steel structure in which step (c) is completed;
(e) forming an elastic film layer by coating an elastic film forming resin on the primer layer;
(f) primary curing step;
(g) forming an anti-deterioration film layer by coating the anti-deterioration film resin on the surface of a steel structure cured with an elastic film layer; And
(h) a second curing step,
The primer resin includes 15 to 25% by weight of styrene-alkyl acrylate copolymer resin, 35 to 50% by weight of ceramic resin and the balance of water,
The elastic film-forming resin is an organic-inorganic composite resin, water-soluble latex, phase change functional material, purification functional composite material, nylon fiber, shrinkage reducing agent and an organic solvent, characterized in that the salt structure, neutralization prevention and waterproof, for the method Eco-friendly surface protection method.
According to claim 1, The organic-inorganic composite resin is a ceramic resin 20 to 25% by weight, urethane-(meth)acrylate-silane copolymer resin 40 to 50% by weight, acrylic emulsion resin 10 to 20% by weight and the balance of organic Containing solvent Eco-friendly surface protection method for the prevention of salt damage, neutralization and waterproofing, steel structure of the steel structure, characterized in that.
The method of claim 2, wherein the urethane-(meth)acrylate-silane copolymer resin is a urethane-(meth)acrylate-silane copolymer resin represented by the following formula (1) salt structure, salt damage, neutralization prevention and Eco-friendly surface protection method for waterproofing and anticorrosion;
[Formula 1]

In Formula 1, R ¹ is a hydrogen atom or a C ₁ ~ C ₃ straight-chain alkyl group or C ₃ ~ C ₅ pulverized alkyl group, R ² is a hydrogen atom, C ₁ ~ C ₃ straight-chain alkyl group, C ₃ ~ C ₅ pulverized alkyl group or

, And R ³ is -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ or -OCH ₂ CH ₂ CH ₂ CH ₃ .
The method of claim 2, wherein the acrylic emulsion resin is characterized in that it comprises a copolymer represented by the formula (2) Environment-friendly surface protection method for preventing, neutralizing and waterproofing the salt structure of steel structures;
[Formula 2]

In Formula 2, R ¹ is a hydrogen atom or a C ₁ ~ C ₃ straight-chain alkyl group, R ² and R ³ are each independently, hydrogen atom or a C ₁ ~ C ₅ straight-chain alkyl group, R ⁴ Is an acetyl group or a diacetyl group, and each of a, b, c and d is an integer from 1 to 50 independently.
The method of claim 1, wherein the ceramic resin is a salt of a steel structure characterized in that it is a polymer obtained by polymerizing a mixture of 100 parts by weight of silicon tetraalkoxide, 400 to 550 parts by weight of methyl methacrylate and 120 to 180 parts by weight of water, Eco-friendly surface protection method for neutralization prevention, water resistance, and corrosion protection.

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