KR100973984B1 - Waterproofing Composition Having Permeation Mechanism - Google Patents

Abstract

The present invention discloses a silicone-based permeable absorption inhibitor and a composite surface treatment method of a transparent paint and a structure using the same.

According to the present invention, the surface cleaning step of cleaning the structure by physical and chemical methods of new and old stone or concrete structure, the absorption prevention step of treating the silicon-based penetrant absorbent on the surface of the cleaned stone or concrete structure, absorption Applying the finishing coating step of painting silicone modified acrylic transparent paint on the surface of prevented stone or concrete structure in order to remove the contamination of stone or concrete structure and to regenerate the texture, and to prevent the absorption of structure, pollution, chloride ion The resistance to penetration, resistance to neutralization, and resistance to freezing and thawing can be greatly improved to maintain and preserve beautiful stone or concrete structures for a long time.

Silicone resin, permeation absorption inhibitor, silicone modified acrylic paint, surface treatment method, eco-friendly

Description

Silicone-based permeation absorption agent, silicone-modified acrylic transparent paint, and composite surface treatment method of structure using same {Waterproofing Composition Having Permeation Mechanism}

The present invention relates to a silicone-based permeable absorption inhibitor, a silicone-modified acrylic transparent paint, and a composite surface treatment method of a structure using the same to increase aesthetics and durability of old stone or concrete structures contaminated with acid rain, air pollutants, and microorganisms. will be.

More specifically, it is washed with masonry and building acidic detergent to regenerate the aesthetics of the surface of the structure, and by applying and penetrating the silicon-based permeable absorbent on the surface to give the structure strong water repellency, the absorbency and chloride ion permeability in the structure Significantly decreases the resistance to freeze-thawing and greatly improves the resistance to neutralization by carbon dioxide gas by re-coating the surface of the structure with a silicone-modified acrylic finish that has excellent adhesion and durability to structures coated with a silicone-based permeation absorber. This is to enhance the aesthetics and durability of stone and concrete structures.

Recently, concrete and stone structures such as high-rise buildings, dams, bridges, etc. are increasing rapidly. Since they are severely polluted by environmental pollutants emitted from automobiles and industrial facilities, and the structures are severely damaged by acid rain, the aesthetic and durability problems of stone and concrete structures are highlighted.

In particular, stone and concrete cultural properties that have been maintained for hundreds and thousands of years in Europe, France, and the United States, Japan, etc. have been severely damaged by automobile smoke and acid rain, and their cultural value is lost. As it has a great influence on living, research on the preservation and cleaning of buildings is being actively conducted.

As the standard of living of the people improves, the demand for high-quality buildings that can be preserved in the long-term is increasing.In order to create a more beautiful and pleasant city environment, interest in cleaning and preventing pollution of the building structures and improving durability is heightened. have.

Contamination of stone and concrete structures does not significantly reduce the strength and durability of the structure compared to chemical degradation (neutralization, salting, alkali aggregate reactions, acid rain, etc.) and mechanical degradation (doodle, breakage, cracking, etc.). It appears in the early stages of various deterioration reactions and is related to mechanical deterioration and causes important problems such as deterioration of asset value of structures.

Methods of removing contamination of stone and concrete structures can be roughly classified into physical methods using high pressure water, iron brushes, grinders, and chemical methods using surfactants, solvents, acids, and alkalis. It is preferable to clean the stone and concrete structures by using appropriate methods selectively according to the type of pollution, the material of the structure and the cleaning conditions, but chemical cleaning methods are widely used in terms of economic efficiency and cleaning effect.

In the cleaning process of stone and concrete structure, it completely removes organic pollutants such as oil, black and paint, inorganic pollutants such as dust, white matter and green juice, vegetable contaminants such as moss and mold, corrosion and neutralization. In addition, it is important not to cause secondary pollution or secondary damage.

On the other hand, the cleaned stone and concrete structures or newly constructed stone and concrete structures, various surface treatment methods have recently been developed in order to improve pollution prevention and durability. Among them, permeability absorption inhibitors such as silicone-based water repellents, coating immersion agents, surface reinforcing agents, etc., are more widely used for surface treatment of stone and concrete structures in Germany and Japan because they have stronger penetration into the substrate and superior water repellency than other surface treatment agents. It is becoming.

Silicone-based penetrant absorbents provide hydrophobicity by dispersing hydrophobic groups of silicon on the surface of inorganic materials such as concrete and inner walls of pores to increase the contact angle with water to 100 ° or more. Water vapor or carbon dioxide gas is known to form a semipermeable membrane for permeation.

Application and impregnation of a permeable absorbent on the surface of stone and concrete not only prevents intrusion of contaminants from the surface of the capillary to the surface of the material, but also prevents the formation of mold and algae since the absorption layer on the surface does not contain moisture. In addition, since the movement of water is inhibited in the surface layer treated with a permeable absorption inhibitor, it also helps to prevent whitening. In addition, permeable absorption inhibitors can be installed in a simple operation compared to finishing materials such as other paints, and can protect the sphere without damaging the texture of the material, so as to preserve the existing stone and concrete structures, as well as concrete It is also widely used in finishing and tiled exterior walls and repairs.

Cleaning is one of the important processes that must be carried out during the preservation process for enhancing durability such as maintenance consolidation and waterproofing of stone and concrete structures.

Therefore, the Cultural Heritage Administration re-emphasized the importance of the cleaning process of buildings by supplementing the [Standard Specification for Repair of Cultural Property Repair Works] in early 2005. Patent Application No. 10-2001-0048429 (2001.08.10) Manufacturing Method], Patent Application No. 10-2005-0024706 (2005.03.25) [Method for manufacturing organic pollutants cleaning stone and building cultural property], Patent Application No. 10-2006-0036460 (April 22, 2006) [For stone and building cultural property Metal non-corrosive acid detergents] and various cleaning agents and methods of using the same have been disclosed.

However, in the above data, the method of manufacturing and using the cleaning agent is presented in detail, but the method of decontamination is not detailed.However, the method of preventing the corrosion caused by the use of the acidic detergent and the subsequent treatment to secure the durability of the stone and the concrete structure cannot be provided. It was.

In addition, the patent application number 10-2006-0047610 (2006.05.26) [polymer coating composition for neutralizing concrete structure and preventing salt], patent application number 10-2007-0047762 (2007.05.16) [Environmental surface protection method of salt, neutralization and waterproofing, anticorrosive function of concrete and steel structure using elastic polymer composite material], and these are methods of painting paint on stone and concrete structure And a method of lining using an epoxy resin mortar or the like.

However, the organic resin paint coating method cannot save the inherent texture of the stone or concrete material, and needs to be repainted every 3 to 5 years, so the maintenance cost is high, and the epoxy resin mortar lining method is complicated in the pretreatment process and the construction cost is high. Therefore, the use range is limited.

On the other hand, recently in Korea Patent Application No. 10-2005-0070481 (2005.08.02) [Permeability waterproofing method for suppressing the degradation of concrete structure], Patent Application No. 10-2005-0059443 (2005.07.02) [Prevent neutralization of concrete structure Preparation of surface protective agent and anti-neutralization method of new building structure and repair building structure using same], Patent application No. 10-2005-0023917 (2005.03.23) [Silicone resin emulsion coating material having water repellent function and waterproof and its Manufacturing Method] Recently, a method of treating a silicon-based permeable water repellent to a stone and a concrete structure has been disclosed.

However, the surface treatment method using the silicone-based water repellent has a strong water repellency and strong penetration in stone and concrete structures, effectively preventing the penetration of water and chloride ions from the outside, thus preventing the structure from freezing and thawing and corrosion of the steel. While the effect of greatly increasing the resistance to the silicone-based water-repellent coating is formed in the membrane form of the air permeability of the concrete structure is not known to significantly improve the resistance. In addition, the silicone (silane) -based water repellent is volatile and deteriorates due to ultraviolet rays, etc., and exhibits excellent water repellency at the initial stage of application, but the effect is greatly deteriorated with time, and thus has to be reprocessed every two to three years. .

In addition, the conventional organic solvent type has problems such as environmental pollution due to volatilized organic solvent after application, working environment and fire risk, and the aqueous type dispersed in water has a low silicon concentration of 50% or less, so 2 to 3 times When painting on a place other than the horizontal surface and the performance is exhibited only when painting, there is a drawback that the dale occurs before penetrating the structure, the penetration is not sufficient, and the surface of the structure is stained.

In addition, the surface of the stone and concrete structure treated with a silicone-based water repellent is not good adhesion with organic polymer coatings such as acrylic, epoxy, urethane, alkyd, etc. currently being distributed, so the finishing method by coating cannot be applied.

And if the purpose is to protect the surface of the stone and concrete structure and prevent the neutralization, it may be considered that high weather resistant acrylic paint is sufficient, but there are surface defects such as cold joint and headboard on the other side of concrete. It has been found that no film is formed so that sufficient protection cannot be provided.

In order to solve the above problems, in the present invention, the surface cleaning step of cleaning the structure by physical and chemical methods of new or old stone or concrete structure, the absorption of treating the silicon-based permeation absorption inhibitor on the surface of the cleaned stone and concrete structure. Anti-treatment step, water-absorbing stone and concrete finish surface coating of silicone-modified acrylic water-based finish is applied sequentially to remove the contamination of the stone and concrete structure and regenerate the texture, to prevent the absorption of the structure It provides a new complex surface treatment method for long-term maintenance and preservation of beautiful stone and concrete structures by greatly improving resistance to pollution, penetration resistance to chloride ions, resistance to neutralization and resistance to freezing and thawing.

According to the method proposed in the present invention, the surface treatment of the stone and concrete structure can effectively clean the surface of the structure while suppressing the corrosion of various metallic materials decorated on the contaminated structure, and the concrete structure from acid rain, carbon dioxide, and various pollutions. It can effectively protect the structure, prevent the corrosion of reinforcement of coastal bridges, breakwaters, waterways and underground structures under water pressure, resistance to neutralization of structures, and penetration resistance against chloride ions. ㆍ Improve the resistance to freezing and melting, and improve and maintain the beautiful effect utilizing the waterproofing effect of the structure and the unique texture of the material.

In addition, the silicone-based permeable absorption inhibitor used in the present invention is water-based, so that there is no concern about environmental pollution and deterioration of the working environment, and has excellent permeability to dense stone and concrete structures, and does not cause stains by tide on the cream. The texture of the concrete intrinsic material has the effect of not damaging.

In addition, the silicone-modified acrylic transparent paint proposed in the present invention is an environmentally friendly material because it is aqueous, and has excellent adhesion to a surface treated with a silicone-based permeation absorber, and is transparent and does not damage the texture of stone and concrete inherent materials. .

Hereinafter, the silicone-based permeable absorption inhibitor and the silicone-modified acrylic transparent paint according to the present invention and the surface treatment method of the structure using the same will be described.

The composite surface treatment method of the structure according to the present invention comprises: 1) a surface cleaning step for cleaning the surface of the structure, 2) an absorption prevention treatment step for applying a permeable absorption inhibitor to the surface of the cleaned structure, and 3) an absorption prevention treatment structure. It includes a finishing coating step of coating the silicone-modified acrylic water-based transparent paint on the surface of the.

In this case, inorganic porous building materials such as concrete, mortar, tile, light foam concrete, brick, stone, etc. are used as the structure to be the object of the present invention.

1) The surface cleaning step of concrete and stone structure is a process to remove latent contamination of the structure. It is a physical method of washing using high water pressure, which is currently used in Korea, and various detergents, solvents, and chemicals. The chemical method can be applied suitably. In particular, the surface treatment process of masonry and concrete buildings with high cultural value or high importance is based on the acid detergents disclosed in Korean Patent Application No. 10-2006-0036460 [Metal noncorrosive acid detergent for stone and building cultural properties]. It is possible to apply a method of cleaning using.

2) In the absorption prevention treatment step of applying the silicone-based permeable absorption inhibitor on the surface of concrete and stone structures, the silicone-based permeability absorption inhibitor using the previously disclosed organic solvent-based aqueous silane or siloxane as the main raw material may be applied. However, the present invention treats a creamy water-based silicone permeable absorbent which has excellent permeability to the concrete structure and does not occur even when applied to a vertical surface.

The aqueous silicone permeable absorption inhibitor to be applied to the present invention comprises (A) alkylalkoxysilane, (B) polyorganosiloxane, (C) emulsifier and (D) water.

R _1x Si (OR ₂ ) _4-x of (A), wherein R ₁ is an alkyl group having 1 to 20 carbon atoms, R ₂ is an alkyl group or hydrogen atom having 1 to 6 carbon atoms, and x is an integer of 1 or 2 In general formula (B), R _3a (OR ₄ ) Si (OH) _c O _{(4-abc) / 2} (wherein R ₃ is an alkyl group having 1 to 20 carbon atoms, R ₄ is an alkyl group having 1 to 6 carbon atoms, a + b + c is 3 or less). As an average composition, it is 0.5 <a <= 2, 0 <b <2.0, 0 <c <2.0, and more preferable compositions are 0.8 <a <= 2, 0 <b <1,7, and 0 <c <0.5.

Examples of R ₁ are an alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, nuclear group, peptyl group, octyl group, nonyl group, decyl group and dodecyl group, cyclopentyl group, cyclonuclear group, 4-ethyl It is a cycloalkaline group, such as a nuclear group, a cyclobutyl group, a norbornyl group, and a methylcyclonuclear group, and may be same or different in a molecule | numerator, and preferable R <_1> is a C4-C10 alkyl group.

Examples of R ₂ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a nucleosil group, and may be the same or different in the molecule, and preferred R ₂ is an alkyl group having 1 or 2 carbon atoms.

Examples of R ₃ include an alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, nuclear group, peptyl group, octyl group, nonyl group, decyl group and dodecyl group, cyclopentyl group, cyclonuclear group, 4-ethyl It is a cycloalkali group, such as a nuclear group, a cyclobutyl group, a norbornyl group, and a methylcyclonuclear group, and may be same or different in a molecule | numerator.

Examples of R ₄ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a nuclear group, and may be the same or different in the molecule, and preferred R ₄ is an alkyl group having 1 or 2 carbon atoms.

On the other hand, the weight ratio (A / B) of (B) component with respect to (A) component in the emulsion of this invention is 50/1-10/1, and it is inferior to a stone and concrete surface beyond this range.

In addition, 60-90 weight% is applied as the total amount of (A) and (B) component in the emulsion of this invention. At 60 wt% or less, the viscosity of the emulsion is low and does not form a cream. At 90 wt% or more, the viscosity of the emulsion is too high, resulting in poor coating workability. Most preferable sum total of (A) and (B) is 70-85 weight%.

It is preferable that the viscosity of (B) component is 10 mPas-2000 mPas at 25 degreeC. At 10 mPas or less or 2000 mPas or more, penetration into the pores of the silane / siloxane component becomes uneven, which is not preferable. The best viscosity is 10 mPas-1000 mPas.

The polyorganosiloxane of (B) is a method of hydrolytic condensation of a mixture of methyltrichlorosilane and dimethyldichlorosilane in the presence of alcohol, or hydrolytic condensation of methyltrialkoxysilane and dimethyldialkoxysilane under an alkali catalyst. It can manufacture by a method and can mix and use two or more types of polyorganosiloxane.

Examples of the emulsifier component (C) include alkyl sulfates having 8 to 18 carbon atoms, alkyl and alkali ether sulfates having 8 to 18 carbon atoms in the hydrophobic group, and having 1 to 40 ethylene oxide (EO) or phosphene oxide (PO) units. And anionic surfactants such as alkylphosphazite, alkylarylsulfonate, monohydric alcohol or alkyl phenol sulfocoacid esters and semiesters having 18 carbon atoms, and the like.

Examples of nonionic surfactants include polyvinyl alcohol, alkyl polyglycol ethers consisting of alkyl groups having 3 to 40 EO units and 8 to 20 carbon atoms, EO / PO block copolymers, ethylene oxide or propylene oxide of alkylamines, and the like. Products, and the like.

Preferred emulsifiers are nonionic surfactants, in particular alkylamine adducts with alkylpolyglycol ethers, ethylene oxide or propylene oxide and polyvinyl alcohols. The polyvinyl alcohol may contain 5 to 20% of vinyl acetate units and have a polymerization degree of 500 to 3000.

The amount of the emulsifier used in the present invention is usually 0.1 to 10% by weight, preferably 0.1 to 5% by weight based on the emulsion.

The emulsion of the present invention is effective when a buffer is used to stabilize the pH within a range of 5 to 8 so that the silane of component (A) is stable against hydrolysis. As the buffer, organic, inorganic acids and bases which are chemically inert with respect to the components of the emulsion may be used. For example, a mixture of sodium carbonate, sodium bicarbonate, sodium hydrogen phosphate, acetic acid and aqueous ammonia and the like may be used, and the amount thereof is 3% by weight of the emulsion weight.

In the range in which the object of the present invention is not impaired, a fungicide, a fungicide, an algae, a microbial agent, a flavoring agent, an anticorrosive agent and an antifoaming agent may be added.

The emulsions according to the invention can be prepared by known methods by those skilled in the art. For example, a method of preparing an emulsion having a very low viscosity from a part of components (A) and / or (B), emulsifiers and most of water, and then adding the remaining portions (A) and / or (B) to emulsify, or All of components (A) and / or (B) are made up of a water-in-oil emulsion as part of water and an emulsifier and the remaining water is added to continue the emulsification to form an oil-in-water emulsion by a phase inversion method. In these emulsification steps, a pressurized emulsifier such as a colloid mill may be used.

The emulsion according to the present invention can be painted by using a brush or a roller or spraying on an inorganic porous building material such as concrete, mortar, lightweight foam concrete, brick, or the like. The amount of the coating is preferably 100 to 250 g / m ² , and since the emulsion is creamy, the required amount of coating can be applied by one coating, and two or more coatings are also possible.

3) The silicone-modified acrylic transparent paint may be applied to the surface of the concrete and stone structure after the absorption prevention treatment using the permeability absorption inhibitor of the present invention.

The finishing coating process that finishes to strengthen the resistance to neutralization by using silicone modified acrylic transparent paint is excellent in adhesive strength, durability and transparency with the base treated with silicone-based penetrant absorbent, and can make the texture of stone and concrete itself. have.

The silicone-modified acrylic transparent paint used in the present invention refers to an emulsion paint obtained by dispersing, emulsifying and dissolving polysiloxane composed of an alkoxysilane compound, an organosiloxane compound or a condensate thereof in an aqueous medium.

The transparent paint of the present invention is composed of a core portion made of a crosslinked polymer and a shell portion made of a non-crosslinked polymer in order to increase the film forming property, compactness and durability of the coating film, and the average particle diameter of the emulsion It is good that it is 50-1000 nm. Such emulsions emulsion-polymerize a monomer mixture containing 0.01 to 5% of a crosslinkable monomer such as divinylbenzene, acryl methacrylate, and polyacrylate in one step, and contain the crosslinkable monomer as a second step in the presence of the polymer. In the presence of polymer particles (seed particles) obtained by polymerizing a monomer-mixture which is not present, an alkoxysilane compound or a low molecular weight organosiloxane is added and condensation reaction is obtained.

As a polymerizable monomer other than the crosslinkable monomer used for 1 and 2 stage superposition | polymerization, aromatic vinyl compounds, such as styrene and ethyl vinylbenzene; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylnuclear chamber (meth) acrylate, cyclonuclear chamber (meth) acrylate, 2-hydroxyl (meth) acrylate, glyc (Meth) acrylic acid ester monomers, such as cydyl (meth) acrylate and N, N- dimethylaminoethyl (meth) acrylate; Unsaturated carboxylic acid acids such as (meth) acrylic acid, maleic acid and maleic anhydride; (Meth) acrylamide, vinyltrimethoxysilane, (gamma)-(meth) acylyl propylpropyl methoxysilane, etc. are mentioned, These can be used together 1 type (s) or 2 or more types.

The weight ratio of the first stage and second stage polymers of the seed particles described above is in the range of 70/30 to 30/70, and the glass transition temperature of the entire seed particle polymer is in the range of -20 to 80 ° C.

As the alkoxy compound and the low molecular weight organosiloxane compound described above, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, r-gly Alkoxysilane compounds such as cydoxypropyltrimethoxysilane, r-mercaptopropyltrimethoxysilane, dimethyldimethoxysilane, and organosiloxane oligomers thereof; and the like, and these may be used alone or in combination of two or more thereof. have.

The addition amount of the alkoxysilane compound and the organosiloxane compound is suitably 10 to 80 g per 100 g of seed particles.

To absorb the alkoxysilane compound and the organosiloxane compound in the seed particles, the alkoxysilane compound and the organosiloxane compound may be added little by little or collectively in the aqueous dispersion in which the seed particles are dispersed, and then stirred well. In order to prevent condensation of the alkoxysilane compound and the organosiloxane compound prior to absorption, the aqueous dispersion is preferably at a pH of 4 to 10, preferably at a pH of 6 to 8 and a temperature of 90 ° C or less, preferably 50 ° C or less. The condensation reaction after absorption controls the degree of polysiloxane polymerization obtained by controlling the reaction temperature and pH.

Silica or fluororesin powder used for removing the gloss of the drawing usually has a particle size of 1.0 to 20 µm and is used about 7 to 15% based on 100 parts by weight of solid content. If it is used less than 5%, the matting effect of the drawing is small, and if it is added 20% or more, the alkali resistance and water resistance of the coating film are lowered. The powder may be added by dispersing in a dispersion machine such as a sand mill using a dispersion resin such as a water-soluble resin, a surfactant, or the like.

A preservative and an adjuvant can be used for this paint in the range which does not impair transparency. Common aids include 3- (3,4-cyclophenyl) -1,1-dimethylurea (diuron or DCMU), 3- (3,4-cyclophenyl) -1-methyloxy-1-methylurea (linueon) Dicyclophenyl urea compounds such as these; Triazine-thio compounds such as 2-methylthio-4-t-butylamine-6-cyclopropylamine-1,3,5-triazine; 2- (4-thiazolyl) -benzoimidazole (thiabenzol), 2-methoxycarbonylaminobenzoimidazole and the like. These can be used 1 type or in combination or 2 or more types.

If necessary, the paint can be used as an antifoaming agent, antiseptic, thickening agent, anti-condensing agent, film forming agent, organic solvent, etc. in a range that does not lose transparency.

[Example]

1. Metal noncorrosive acid detergent for cleaning stone and concrete structure

Metal non-corrosive acid detergent for washing stone and concrete structures proposed in the present invention is 1.0% by weight of polyoxyethylene alkyl ether nonionic surfactant (LE1020), 3.0% by weight of H ₂ O ₂ (30% by weight), HCl (35 % By weight) 3.5% by weight, 0.01% by weight of cetyl ammonium chloride, 0.01% by weight of quinoline, 0.01% by weight of BTA, 0.02% by weight of zinc chloride, and 92.45% by weight of water were used.

2. Silicone Permeable Absorption Agent

Polyorganosiloxane component (B) a viscosity of about 30mPas at 25 ℃ formula _{CH 3 (Si (OC 2 H} 5) 0.8 O 1 .1 2g and isopropyl is an ethylene oxide unit as an emulsifier (C) 10 of tridecyl alcohol 0.13 g of glycol ether and 10 g of water (D) were stirred at high speed, and 38 g of isooctyltrimethoxysilane (iC8) was divided into four times as alkylalkoxysilane component (A) and stirred at high speed to prepare an aqueous silicone water repellent treatment agent. .

3. Silicone modified acrylic transparent paint

50 g of deionized water and 2 g of SDBS (sodium dodecylbenzenesulfonic acid) were added to a 2 L four-necked flask A, and heated to 80 ° C. to purge and dissolve the N ₂ gas to form an A solution.

20 g deionized water, 3.5 g SDBS, 0.15 g APS (ammonium peroxydisulphate) was added to 500 mL flask B, and the mixture was stirred well, followed by 7.5 g of cyclonuclear methacrylate, 21.9 g of methyl methacrylate and 7.5 n-butyl acrylate. g, 12.9 g of 2-ethylnucleosil acrylate and 0.2 g of 1,6-nucleic acid diol acrylate are added and stirred well to form a B emulsion.

The B emulsion is stirred in a flask containing A solution over 2 hours with stirring and further reacted at 80 ° C. for 1 hour after the drop is finished.

20 g deionized water, 3.5 g SDBS, 0.15 g APS was added to 500 ml flask C and stirred to form a foam, followed by 7.5 g of cyclonuclear methacrylate, 27.5 g of methyl methacrylate, and 4.5 g of n-butylacrylate. 5.0 g of ethyl nuclear acrylate, 2.5 g of di-acetoacrylamide, 2.0 g of 2-hydroxyethyl acrylate, and 1.0 g of acrylic acid are added thereto, followed by stirring to form a C emulsion.

C emulsion is added to the flask containing A solution over 2 hours and then further reacted at 80 ° C. for 1 hour.

The solution A was cooled to 25 ° C., neutralized to pH 7 with ammonia water, 10 g of phenyltrimethoxysilane was added thereto, stirred for 1 hour, heated to 80 ° C., and reacted for 3 hours to obtain a transparent coating. Used.

4. Production of specimen

According to KS F 5109 (mechanical mixing method of hydraulic cement paste and mortar), a mortar of a combination of cement: fine aggregate: water = 1: 3: 0.5 (mass ratio) was mixed and formed into 100 × 100 × 400 mm. After molding 1 day wicking curing (20 ℃, 90% RH) + 6 days in water curing (20 ℃), mortar specimens were cut into 100x100x100mm and used for 28 days air curing (20 ℃, 60% RH) as a substrate. .

Three days before the end of curing, the surface other than the permeable absorbent coating surface (cutting surface 100x100mm) was sealed with epoxy resin, and after the completion of curing, the permeable absorbent and the silicone-modified acrylic transparent paint were applied twice (200 g / m ² ). After application, room temperature curing (20 ° C., 50% RH) specimens were prepared for 14 days. The test results are shown in Table 1 below.

(1) Freeze-thawing test specimen

Test mortar was molded into 40 x 40 x 160 mm and cured for 28 days, and 5 days except the permeable absorbent coating surface (40 x 160 mm) 3 days before the end of curing were sealed with an epoxy resin and used as specimens.

(2) Test specimen for accelerated weathering test

The 40 x 40 x 160mm mold was used to mold a 40 x 40 x 20mm test mold for curing for 28 days, and 3 days before the end of curing, the surface except for the permeable absorbent coating surface (40 x 40mm) was sealed with epoxy resin to be used as test specimen. It was.

5. Evaluation method

(1) Glossiness: 60 ° reflectance measurement

(2) Water resistance: After immersing each test body in a constant temperature water bath at room temperature for 20 days for 7 days, the water absorption was measured and the coating state was determined (◎: no abnormality, ○: swelling, discoloration is seen but no problem in practical use, △: swelling, Discoloration occurs in part, ×: swelling, discoloration is recognized)

(3) Alkali resistance: Visually determine the state of coating after immersion in a water tank filled with saturated calcium hydroxide solution at 20 ° C for 30 days (◎: No abnormality, ○: Swelling, discoloration, glossiness, but practically not impaired) , △: swelling, discoloration, gloss occurs in part, ×: swelling, discoloration, gloss are recognized)

(4) Interlayer adhesion: Test the adhesion between the first layer and the second layer coated with the aqueous waterproofing material twice with each test body by cross-cutting method and observed with a magnifying glass.

(Double-circle): No peeling phenomenon ((circle): A peeling is seen to a part of coating film, but practically does not interfere, (triangle | delta): Peeling generate | occur | produces to 25% or less, x: Peeling generate | occur | produces 25% or more)

(5) Accelerated weather resistance: Each test specimen was applied to a sunshine weather meter for 2000 hours and observed for its coating state. , ×: swelling, discoloration recognized)

(6) Wet colorability: Observe whether the color of the wetted sheet formed by the coating was observed with respect to the color on the flexible plate before coating (◎: No abnormality, ○: Discoloration was seen slightly, but practically no problem, △: Discoloration occurred in part, × Swelling, discoloration is recognized)

(7) paintability

The emulsion was applied with a brush at 200 g / m ² with respect to the vertical surface of the concrete specimen, and it was observed whether the emulsion, which was applied until 3 minutes after application, became a drop of water and fell vertically.

(8) Penetrating depth of penetration inhibitor

Apply 200 g / m ² of emulsion to the specimens and air cure (20 ℃, 60% RH) for 3 days, cut the central part of the concrete and spray distilled water to remove the depth of the wall from the surface of the specimen. The location was measured and the average value was taken as penetration depth.

(9) Chlorine ion permeability

100x100x400 mm of one side of the specimen was sealed with an impermeable membrane to a height of 5 mm, and the specimen was placed in a sealed portion for 4 hours with NaCl 4% solution, followed by daughtering and drying for 23 hours. Was dried, sampled at a depth of 0 ~ 9mm from the surface of the specimen, pulverized sufficiently, eluted with distilled water and the concentration of chlorine ion (Cl-) was measured according to the JCI SC4 method.

(10) Neutralization Promotion Test

100 x 100 x 400mm 6 total silicone type permeability absorbing agent to 200g / m ³ is applied by the carbon dioxide concentration in the specimen as in the accelerated neutralization tester adjusted to a 5%, 20 ℃, 60% RH 16 jugan facilitate neutralization test side of the specimen Then, the center portion was cut and sprayed with a 1% phenolphthalein ethanol solution to measure 10 depths from the surface of the portion discolored in red, and the average value was taken as the neutralization depth.

(11) resistance to freezing and thawing

In accordance with JIS A 1148 (Concrete Freeze Melting Test Method) A method (Underwater Freeze Melting Test Method), a freeze-thawing test of 300 specimens was carried out, and the mass reduction rate of the specimens was determined in a predetermined cycle.

Metric Normal
Specimen wash
Specimen Washing + Water Repellent Treatment Washing + Water repellent + Finishing specimen (1) glossiness 7.7 11.4 16.4 24.2 (2) Water resistance (absorption rate) (1.2%) (1.3%) ○ (0.3%) ◎ (0.2%) (3) alkali resistance - - ◎ ◎ (4) interlayer adhesion - - ◎ ◎ (5) accelerated weather resistance - - ○ ◎ (6) wetting - - ◎ ◎ (7) paintability - - Boreal radish Boreal radish (8) penetration depth of penetration inhibitor - - 9.4 mm 9.8 mm (9) Chlorine ion permeability [kg / m ³ ] 4.2 6.0 0.1 0.1 (10) Neutralization Promotion Test [mm] 6.5 7.0 4.6 0.1 (11) resistance to freezing and thawing 15% 18% -4% -3%

The structure of the present invention is a structure constructed of an inorganic porous building material such as concrete, mortar, tile, light foam concrete, brick, stone and the like. That is, it removes contaminants from structures such as stone cultural properties and concrete buildings, bridges, dams, etc., effectively protects concrete structures from acid rain, carbon dioxide, and various pollutions, and protects coastal bridges, breakwaters, waterways, and water pressures affected by nonexistent salts. It can be applied to prevent reinforcing corrosion of underground structures, to resist neutralization of structures, to penetrate resistance to chloride ions, to resist freezing and thawing, and to enhance and maintain the beauty of the structure's waterproofing effect and material uniqueness. .

Claims (14)

delete delete A silicone-modified acrylic transparent paint obtained by dispersing, emulsifying and dissolving polysiloxane composed of an alkoxysilane compound, an organosiloxane compound or a condensate thereof in an aqueous medium. The method according to claim 3, Transparent paint is a silicone-modified acrylic transparent paint consisting of a core portion made of a crosslinked polymer, and a shell portion made of a non-crosslinked polymer. The method according to claim 3 or 4, The monomer-mixture containing the crosslinkable monomer is emulsion polymerized to form a one-step polymer, and the monomer-mixture not containing the crosslinkable monomer is polymerized in the presence of the polymer to form a two-step polymer, A silicone-modified acrylic transparent paint, which is condensed by adding an alkoxysilane compound or a low molecular weight organosiloxane in the presence. The method according to claim 5, The weight ratio of the two-stage polymer to the first-stage polymer is 70/30 ~ 30/70 silicone modified acrylic transparent paint. The method according to claim 5, Crosslinkable monomer is a silicone-modified acrylic transparent paint containing at least one or more of divinylbenzene, acryl methacrylate, polyhydric acrylate. The method according to claim 5, The polymerizable monomer is at least one of styrene, an aromatic vinyl compound, (meth) acrylic acid ester monomer, unsaturated carboxylic acid, (meth) acrylamide, vinyltrimethoxysilane, and γ- (meth) acylyloxypropyltrimethoxysilane. Silicone modified acrylic transparent paint consisting of the above. A surface cleaning step of cleaning the surface of the structure; An absorption prevention step of applying a silicone-based permeable absorption inhibitor comprising an alkylalkoxysilane, a polyorganosiloxane, and an emulsifier on the surface of the cleaned structure; A composite surface treatment method of a structure comprising a finishing coating step of coating the silicone-modified acrylic transparent paint of claim 3 or 4 on the surface of the structure to prevent absorption. The method according to claim 9, The composite surface treatment method of the structure whose total amount of the said alkyl alkoxysilane and the said polyorganosiloxane is 60 to 90 weight% of the whole composition. The method according to claim 9, The emulsifier is a composite surface treatment method of a structure comprising any one of alkyl polyglycol ether, ethylene oxide, alkylamine adduct with propylene oxide or polyvinyl alcohol. The method of claim 11, The emulsifier is 0.1 to 10% by weight based on the composition of the composite surface treatment method. The method according to claim 9, Composite surface treatment method of a structure further comprising a buffer to stabilize the pH within the range of 5 to 8 against the hydrolysis of the transparent paint. 14. The method of claim 13, The buffer is a composite surface treatment method of the structure consisting of a mixture of at least one or more of sodium carbonate, sodium hydrogen carbonate, sodium hydrogen phosphate and acetic acid and ammonia water.