KR100915774B1 - Waterproof agent for a facing surface containing polymethylsiloxane solution and a method of waterproof at a facing surface using the same - Google Patents

Abstract

The present invention relates to a waterproofing agent and a crosslinking waterproofing method for the waterproofing of the cross-linked material such as a bridge mainly composed of concrete, the inorganic permeability including a polymethylsiloxane solution excellent in adhesion and storage stability on the inorganic permeable waterproofing agent having a silicon component Apply the waterproofing agent, and apply polyamine-polyurethane copolymer having excellent heat resistance, adhesion, chemical resistance and waterproofing property on it, and then treat silica sand or aggregate as necessary to handle defects caused by lifting of waterproofing agent or concrete. By preventing the defects caused by various factors such as damage due to the coating film damage caused by the water in order to prevent damage to the floor surface of bridges, buildings, roads, etc. due to water or salt and to reduce the damage caused by leakage.

Description

Waterproofing agent for a facing surface containing polymethylsiloxane solution and a method of waterproof at a facing surface using the same

The present invention relates to the waterproofing of the bridges of the main body of the concrete, such as bridges, roads, more specifically, the present invention provides an inorganic permeable waterproofing agent comprising a polymethylsiloxane solution similar to the components of the concrete, and The inorganic permeable waterproofing agent is first applied to a polyamine-polyurethane copolymer, and it is related with the crosslinking waterproofing method which consists of a process of apply | coating 2 or more times on it, and spraying a silica sand or aggregate as needed.

In general, in the concrete used for bridges, salt damage, cracking and neutralization of alkali aggregate-reacted concrete are the main causes of shortening bridge life. Both of these cause corrosion of concrete and rebar due to water intrusion.

In recent years, due to the trend toward longer bridge structures, special bridges such as the West Sea Bridge, Yeongjong Bridge, Gwangan Bridge, and Incheon Bridge are being built in Korea. In the case of such long bridges, the waterproofing of bridges has become more important because they are designed with a structure that is easy to vibrate against dynamic loads such as earthquakes, winds, vehicles, etc., and the bridges are lighter.

The currently used cross-section waterproofing method can be represented by penetration waterproofing, coating waterproofing, sheet waterproofing according to the waterproofing method. The waterproofing agent used for waterproofing is mainly made of silicone and diluted products. They have been used in simple bridge structures with a penetration depth of less than 1 mm, but their performance is significantly lower after six months, making them difficult to use in critical structures. In case of waterproofing of coating, it is divided into urethane or epoxy waterproofing agent according to material. Urethane waterproofing agent has the advantage of excellent elasticity and crack resistance, but weak to moisture and poor adhesion to concrete frequently occurs defects, there is a variation in the quality of the formulation and difficult in winter construction. In the case of epoxy waterproofing agent, there is no resistance to cracking and the coating film is susceptible to impact. If water penetrates into the defect, the entire coating film is lifted.

On the other hand, a number of documents are known in connection with the composite waterproof method used for general concrete structures. Patent registration 10-0351109 is characterized in that the acrylic waterproofing agent is manufactured by reinforcing the coating protective agent on the acrylic water-soluble penetration waterproofing agent which is an organic waterproofing agent, but the use of the coating protective agent is a method already used in the bridge waterproofing method. Patent registration 10-0238994 discloses a composite waterproofing method for applying a liquid polyurethane on an asphalt sheet, and Patent Registration 10-0329661 discloses a method for treating a rubber asphalt waterproofing agent on a thin film polymer using a vinyl acetate resin. In addition, Patent Registration 10-0369465 discloses a composite waterproofing method applying a polyalkylene organic polymer penetration waterproofing layer, rubber asphalt primer layer, polyethylene film sheet layer, etc., Patent Registration 10-0278173 is applied a polyethylene sheet on the rubber asphalt. The composite waterproof method is disclosed. In addition, Patent Registration 10-0166114 uses a fabric sheet on rubber asphalt, and Patent Registration 10-0288327 discloses methods using rubber sheet on asphalt.

When the permeable waterproofing agent was used in the method described in the above prior art document, vinylacetate or a water-soluble acrylic polymer was used as the permeable waterproofing agent to be applied first. However, in the case of these polymers, the penetration performance is lowered, and the polymer component itself is broken by reacting with the alkali component of concrete, so that the waterproof performance is deteriorated with time. In addition, the coating film component used the conventional urethane or asphalt component, and the sheet used the rubber-type product. However, since the temperature of the molten ascon applied to the upper portion of the coating film is 150 to 180 ° C., there is a problem in that the coating film is damaged by the high temperature of the ascon when using a material that is weak in heat such as urethane.

The present invention was developed to solve the problems of the prior art, to prepare an inorganic permeable waterproofing agent comprising a polymethylsiloxane solution similar to concrete components, and to apply the inorganic permeable waterproofing agent to the object to be waterproofed thereon By coating a polyamine-polyurethane coating waterproofing agent is to provide a waterproof method that the waterproof layer is not damaged by various external stimuli.

Permeable waterproofing agent according to the present invention is penetrated more than 4mm deep from the concrete surface, so that even if the concrete is damaged by external shocks to maintain the waterproofing function, polyamine-polyurethane coating waterproofing agent with elongation vibration or microcracking of the concrete structure Since it has a resistance to, it can exhibit excellent waterproofing. In the present invention, two different coating film waterproofing agents are applied in a double manner to obtain a superior waterproofing function than the conventional waterproofing method.

In a first aspect of the invention, the invention relates to tetraethyl ortho silicate in polyoxyethylene octylphenyl ether, polyethylene oxide, polypropylene oxide, And hydrolysis with hydrochloric acid and phosphoric acid under a neutral surfactant selected from polyethylene glycol, followed by further hydrolysis by addition of dichlorodimethylsilane (Me ₂ SiCl ₂ ) and hydrochloric acid to provide a polymethylsiloxane solution.

In a preferred embodiment, the invention is selected from polyoxyethylene octylphenyl ether, polyethylene oxide, polypropylene oxide, and polyethylene glycol in 100 parts by weight of tetraethyl ortho silicate in a solvent consisting of at least 95% by weight of alcohol and the balance of water 1 to 3 parts by weight of a neutral surfactant, 3 to 5 parts by weight of hydrochloric acid, and 3 to 5 parts by weight of phosphoric acid are added to react at room temperature to 60 ° C, and then 10 to 20 parts by weight of dichlorodimethylsilane and 0.1 to 1 parts by weight of hydrochloric acid In addition, a polymethylsiloxane solution obtained by further reacting at room temperature to 60 ° C is provided.

In a second aspect of the present invention, the present invention provides an inorganic permeable waterproofing agent mainly composed of the polymethylsiloxane solution obtained as described above.

In a third aspect of the present invention, the present invention provides a cross-linking waterproofing method for applying the inorganic permeable waterproofing agent and the polyamine-polyurethane copolymer according to the present invention on a subject requiring waterproofing.

In a preferred embodiment, the crosslinking waterproofing method according to the present invention comprises first applying the inorganic permeable waterproofing agent according to the present invention on a structure in need of waterproofing; A polyamine-polyurethane copolymer is applied thereon at least twice, preferably second or third; And if necessary, applying silica sand or aggregate thereon.

The present invention provides an inorganic permeable waterproofing agent that contains a silicon component similar to concrete and can penetrate deeply into a concrete-based material to exhibit excellent waterproofing function. In addition, the present invention is excellent in adhesion and waterproofing ability to the subject through the step of first coating the inorganic permeable waterproofing agent and then coating the polyamine-polyurethane copolymer obtained by polymerizing polyurethane and polyamine amide thereon at least two times. And it provides the effect of providing a waterproof method that minimizes the occurrence of defects.

1 is a diagram showing a schematic cross-sectional view of a test body coated with ascon on a concrete test body constructed by a waterproofing method according to a preferred embodiment of the present invention.

The cross-section waterproofing method according to the present invention is made by first coating the inorganic permeable waterproofing agent according to the present invention with a roller or a spray on the surface of the object from which foreign substances have been removed, and after the coating surface is dried, the second coating with a polyamine-polyurethane copolymer. . If desired, the polyamine-polyurethane copolymer may be optionally further tertiaryly coated on the secondary painted surface, and silica sand or aggregate may be applied thereon. At this time, it is most preferable to use the silica sand 2 or 3 yarn used or mixed respectively. If there are many fine pores on the surface of the second coating, a mixed filler of silica powder, mica and talc is mixed with the polyamine-polyurethane copolymer, and if the surface of the substrate is good, It is possible to paint only the polyamine-polyurethane copolymer without adding the filler.

The mixed filler of the present invention is made by mixing silica powder, mica, and talc, each of which comprises 90% to 95% silica powder, 2% to 10% mica, and 2% to 10% talc by weight. It consists of. The finer the particle size of the silica powder used for the filler is preferable. If you use 3% to 5% of mica based on the total weight of the filler, the microcracks of the conductor can be more effectively compensated for, and 2% to 5% of talc can further enhance the cohesion between the copolymer and the filler. have.

Hereinafter, the cross-section waterproofing method according to the present invention will be described in more detail.

First, remove foreign substances on the base surface of the substrate such as concrete, and the inorganic permeable waterproof agent according to the present invention is coated with a roller or spray (primary coating). Curing time after the primary coating may vary depending on temperature and humidity, but typically takes 3 to 4 hours.

Second, large holes or cracks are pre-filled.

Third, to 100 parts by weight of the polyamine-polyurethane copolymer according to the present invention, 20 to 100 parts by weight of the mixed filler of silica powder, mica, and talc are mixed well with stirring, and then coated on the subject by roller or spray (2 Car seal). If the surface condition of the conductor is uniform during the second coating, paint only the polyamine-polyurethane copolymer without using a mixed filler. The curing time after the second coating is usually 4-8 hours.

Fourth, a coating process such as secondary coating is repeated as necessary to obtain better interlayer adhesion (tertiary coating). It is preferable that the third coating is performed within 48 hours after the second coating. If the third coating is performed after 48 hours after the second coating, the desired interlayer adhesion may not be obtained.

Fifth, the silica sand or aggregate is sprayed on the second or third painting surface. Scattering siliceous sand or aggregates on the bridge can increase the adhesive strength by increasing the surface area while providing an anti-slip effect during the work.

The inorganic permeable waterproofing agent used in the primary coating according to the present invention contains a polymethylsiloxane solution as a main component, and is used for waterproofing the cross-sections of various subjects such as concrete bridges, building walls, and roads. The polymethylsiloxane solution is composed of tetraethyl ortho silicate in a solvent consisting of at least 95% by weight of lower alcohol having 1 to 4 carbon atoms and a residual amount of water, preferably in a solvent consisting of at least 95% by weight of isopropyl alcohol and a residual amount of water ( Tetra ethyl ortho silicate) is hydrolyzed with hydrochloric acid and phosphoric acid under neutral surfactants such as polyoxyethylene octylphenyl ether, polyethylene oxide, polypropylene oxide, polyethylene glycol, and then added further by adding dichlorodimethylsilane and a small amount of hydrochloric acid. It is prepared by decomposition (Scheme 1).

Scheme 1

When the tetraethyl ortho silicate compound is hydrolyzed with alkali, the strength may decrease after curing. In the present invention, hydrolysis is performed under acidic conditions other than alkali to prepare a nano-silica solution, and dichlorodimethylsilane and a small amount are added thereto. Hydrochloric acid was added to further hydrolyze to prepare a polymethylsiloxane solution.

The secondary waterproofing agent according to the present invention is a polyamine-polyurethane copolymer, and is preferably a polyamine-polyurethane copolymer prepared according to Korean Patent No. 10-694200, which is a registered patent of the present inventor. The coating of the polyamine-polyurethane copolymer on the surface of the subject provides excellent heat resistance and chemical resistance adhesion of the coating film and excellent waterproofing effect. The patent is incorporated herein by reference, but the following briefly describes the characteristic configuration of the polyamine-polyurethane copolymer so that the present invention can be more clearly understood.

The polyamine-polyurethane copolymer according to the present invention has a pH of 6 to 8, a viscosity of 250 to 400 cps, and a specific gravity of 1.0 to 1.1. Polyol was reacted with isocyanate in the reaction solvent to prepare a polyurethane having 3 to 10% of the -NCO functional groups of isocyanate remaining, and then polyamine amide was added to react for 30 minutes to 5 hours at a temperature of 50 ° C to 80 ° C. A new type of polyamine-polyurethane copolymer having a structure is prepared.

Methods of making polyurethanes by reacting polyols with isocyanates are well known to those skilled in the art. Polyols are largely divided into polyester polyols or polyether polyols, both of which may be used. It is preferable that the molecular weight of a polyol is 100-800. When the molecular weight is less than 100, the impact resistance and elongation of the obtained copolymer waterproofing agent are low, and thus the adhesive strength is lowered. When the molecular weight is larger than 800, the strength and heat resistance of the copolymer waterproofing agent obtained are poor. It is also possible to mix and use two or more of the polyols having a molecular weight in the above range. The isocyanate may be all isocyanate generally used for polyurethane production, but polymethylene polyphenyl isocyanate having a molecular weight of 50 to 300 is preferable.

The content ratio of polyol and isocyanate is determined according to the type of polyol and isocyanate used, which can be easily determined by those skilled in the art. The equivalent ratio of NCO / OH of the prepolymer is preferably 0.9 to 0.97 so that 3% to 10% of the -NCO functional groups of the isocyanate remain in the polyurethane obtained. If the remainder of the -NCO functional group is less than 3%, it is likely to cure during the reaction with the polyamine amide, and if it exceeds 10%, the physical properties of the final product are poor. The solvent for the reaction of the polyol and the isocyanate is preferably a general aromatic solvent such as toluene and xylene.

The reaction temperature of the polyol and isocyanate is between room temperature and 80 ° C. If the reaction temperature is higher than 80 ℃ the molecular weight of the copolymer produced increases the adhesive strength, if the temperature is too low below room temperature, the strength of the initial coating film is good but has a weak disadvantage in impact. Process conditions for other polyurethanes, such as catalysts and solvents required for the reaction, are in accordance with general polyurethane production methods, which can be readily determined by one skilled in the art.

The polyurethane thus obtained is not heat resistant and thus cannot function properly as a crosslinking waterproofing agent. In the present invention, the resulting polyurethane is reacted with polyamine amide at a temperature of 50 ° C. to 80 ° C. for 30 minutes to 5 hours to prepare a copolymer. The polyamine amide is preferably an unsaturated compound having an amine value of 25 to 35 and a refractive index of 1400 to 1500.

The polyamine amide is added at 0.5 to 5 parts by weight based on 100 parts by weight of polyurethane. If it is added less than 0.5 parts by weight, the desired heat resistance is not obtained, and if it is added more than 5 parts by weight, the adhesive strength is lowered and the shock is weak. The copolymer waterproofing agent thus prepared has the most excellent heat resistance, so it is most suitable for waterproofing bridges. In addition to bridges, the copolymer waterproofing agent may be widely used as a general waterproofing agent for waterproofing roads or building exterior walls.

Through the following examples, the present invention will be described in more detail.

The present invention is described in more detail by the following examples, the following examples are not intended to limit the scope of the invention only because of illustrating the present invention.

Example

Preparation of Nano Silica Solution

Example 1

Add 100 g of tetraethyl ortho silicate to a mixed solvent of 200 g of isopropyl alcohol and 5 g of water, add 1.0 g of Triton X-100 (Sigma) while stirring at room temperature, add 3.0 g of phosphoric acid and 3.0 g of hydrochloric acid dropwise at 50 ° C for 30 minutes. Hydrolysis was carried out to prepare a nano silica solution.

Comparative Examples 1 to 4

As shown in Table 1, a polymethylsiloxane solution was prepared in the same manner as in Example 1 except that hydrolysis was performed using another acid instead of phosphoric acid and hydrochloric acid.

The adhesion of the polymethylsiloxane solution obtained according to Example 1 and Comparative Examples 1 to 4 was measured according to KS D 6711-1992, and the storage stability of the solution was stored for 3 months at room temperature, followed by precipitation formation and gelation. The presence or absence was measured. Table 1 shows the results of adhesion and storage stability measurements. In Example 1 obtained by hydrolysis with a mixed acid solution of phosphoric acid and hydrochloric acid, adhesion and storage stability were the best.

Table 1

Kind of the mountain Adhesion test result ¹⁾      Remarks Example 1 Hydrochloric acid + phosphoric acid ○ Excellent storage stability and adhesion Comparative Example 1 Hydrochloric acid (HCl) △ Storage stability but poor adhesion Comparative Example 2 Sulfuric acid (H ₂ SO ₄ ) × Very weak adhesion Comparative Example 3 Phosphoric Acid (H ₃ PO ₄ ) ○ Adhesion but gelling. Comparative Example 4 Polyphosphoric Acid (PPA) △ Storage stability but weak adhesion

1) Adhesion test method: After applying the test solution on the glass surface, cut 10 lines at 1.0mm intervals horizontally and vertically according to the method of KS D 6711-1992. (Circle) and less than 98%, and 95% or more of normal ((triangle | delta)), and when less than 95% were attached, it determined as bad (x).

100 g of the nano-silica solution prepared in Example 1 was measured according to the test method (temperature and reaction time) shown in Table 2 below, and the results were observed.

TABLE 2

Test Methods Adhesion Test Results Remarks Temperature Reaction time 40 ℃ 30 minutes × The reaction does not end 60 minutes × 50 ℃ 30 minutes ○ 60 minutes △ Long reaction time causes side reaction 60 ℃ 30 minutes △ Larger particles after 30 minutes 60 minutes × 80 ℃ 30 minutes × Precipitation in solution 60 minutes ×

Example 2: Preparation of Polymethylsiloxane Solution Containing Nano Silica Solution

18 g of dichlorodimethylsilane (Me ₂ SiCl ₂ ) was slowly added dropwise to 100 g of the nano-silica solution prepared in Example 1, 0.1 g of 10% concentrated hydrochloric acid (36.5%) was added thereto while stirring at room temperature, followed by stirring for 30 minutes. It was raised to 60 ℃ and stirred for 2 hours to prepare a polymethylsiloxane solution containing a nano silica solution.

The water absorption, penetration depth, and water permeability tests of the polymethylsiloxane solution obtained in Example 2 were carried out according to the Korean Industrial Standard Test Method KS F 4930-02, and the results are shown in Table 3.

TABLE 3

Test Items Test result Based on KSF 4930-02 Appearance after application clear clear Water absorption Standard condition 0.04 0.5 or less After alkali resistance test 0.06 0.5 or less After low temperature high temperature repeat resistance test 0.04 0.5 or less           Penetration depth 4.7 4.0 or higher        Permeability (Pitching Ratio) 0.21 0.1 or less

Example 3: polyamine cross-section waterproofing method

100 g of toluene and 100 g of polyester polyol (PP-400) were added to the reactor, followed by stirring. Then, 150 g (M-100) of polymethylene polyphenyl isocyanate was added slowly and stirred at room temperature for 1 hour, and then the temperature was raised to 50 to 80 ° C. and stirred for 4 hours. Give it. 5g of polyamine amide was added to this solution, and it was made to react for 2 hours, and 355g of polyamine-polyurethane copolymers were obtained.

Example 4 Bridge Waterproofing Method

Step 1: After removing the foreign matter on the concrete surface, the polymethylsiloxane solution prepared in Example 2 with a roller of 0.1 ~ 0.2Kg / m ² Apply in amounts.

Step 2: After 3-4 hours, the polyamine-polyurethane copolymer prepared in Example 3 is coated on the concrete surface with an roller in an amount of 0.1-0.2 Kg / m ² . After coating, the curing time takes 4 to 8 hours, and then the coating is performed with an undiluted polyamine-polyurethane copolymer within 48 hours. At this time, if the top coat is performed after 48 hours, the interlayer adhesion may be reduced. After coating the top coating, apply silica sand 2-3 in the amount of 0.3 ~ 1.0 Kg / m ² in consideration of adhesion with ascon.

According to the waterproofing method of the present invention as described in Example 4, the water permeability of the crosslinked waterproof concrete construction body was tested according to the Korean Industrial Standard Test Method KS F-4930-02, and the water permeability was 0.02. 5 times better). From this, it can be seen that the waterproofing method according to the present invention is much more effective in the water permeability test than when using the permeable waterproofing agent alone.

Various modifications and variations are possible without departing from the spirit and scope of the invention, and modifications apparent to those skilled in the art to which the invention pertains are included in the following claims.

Claims (8)

Tetraethyl ortho silicate in hydrochloric acid under neutral surfactant selected from polyoxyethylene octylphenyl ether, polyethylene oxide, polypropylene oxide, and polyethylene glycol in a solvent consisting of at least 95% by weight of lower alcohols having 1 to 4 carbon atoms and residual water. And a polymethylsiloxane solution prepared by hydrolysis with phosphoric acid, followed by further hydrolysis by addition of dichlorodimethylsilane and hydrochloric acid. Neutral interface selected from polyoxyethylene octylphenyl ether, polyethylene oxide, polypropylene oxide, and polyethylene glycol in 100 parts by weight of tetraethyl ortho silicate in a solvent consisting of at least 95% by weight of lower alcohol having 1 to 4 carbon atoms and a residual amount of water. 1 to 3 parts by weight of the active agent, 3 to 5 parts by weight of hydrochloric acid, and 3 to 5 parts by weight of phosphoric acid are added to react at room temperature to 60 ° C, and then 10 to 20 parts by weight of dichlorodimethylsilane and 0.1 to 1 part by weight of hydrochloric acid are added. Polymethylsiloxane solution obtained by making it react further at room temperature-60 degreeC. An inorganic permeable waterproofing agent comprising the polymethylsiloxane solution according to claim 1. First applying an inorganic permeable waterproofing agent according to claim 3 on the subject to be waterproofed (primary coating); And applying a second polyamine-polyurethane copolymer after the first coating (secondary coating). 5. The method of claim 4, further comprising the step of applying a third (third coat) of the polyamine-polyurethane copolymer on the subject within 48 hours after the second coat. The method of claim 4, further comprising spraying silica sand or aggregate on the subject after the second coating. Polymethylsiloxane solution for primary application; And a polyamine-polyurethane copolymer for secondary to tertiary coating, wherein the polymethylsiloxane solution is a polymethylsiloxane solution according to claim 1 or 2, wherein the polyamine-polyurethane aerial The copolymer is a polyamine-polyurethane copolymer having a viscosity of 250 to 400 cps and a specific gravity of 1.0 to 1.1 prepared by polymerizing 100 parts by weight of polyurethane and 0.5 to 5 parts by weight of polyamine amide at a temperature of 50 to 80 ° C. for 30 minutes to 5 hours. Interstitial Repellent Kit. The method of claim 5, further comprising spraying silica sand or aggregate on the subject after the third coating.