KR101870361B1 - Eco friendly-high functional polymer waterproof material for concrete using shell powder - Google Patents

Abstract

The present invention relates to an eco-friendly high-performance polymer composite waterproofing agent using shell powder and a concrete structure using the same. More specifically, the present invention relates to an eco-friendly high-performance polymer composite waterproofing agent utilizing eco-friendly and multi-functional shell powder capable of enhancing mechanical and chemical properties of a concrete structure, and a concrete structure using the same.

Description

TECHNICAL FIELD [0001] The present invention relates to an eco-friendly high functional polymer waterproofing material for concrete using a shell powder,

The present invention relates to an environmentally friendly high functional polymer composite waterproofing agent utilizing shell powder capable of improving waterproofness and durability of a concrete structure with little emission of heavy metals and total volatile organic compounds, and a concrete structure using the same.

Concrete is a porous structure having continuous capillary voids, and it is corroded due to complex causes such as freezing and thawing, neutralization, and saltation depending on the external environment, resulting in a decrease in durability. This is not only a deterioration in the performance of the concrete structure but also cracks and peeling, which leads to leakage, and thus requires a separate waterproof layer.

Epoxy, acrylic, and urethane based materials are excellent in color, initial adhesion and chemical resistance. However, it has poor affinity with concrete, lifting of coating film occurs, durability is low, and volatile organic solvents are used to cause accidents and environmental pollution. Some modified waterproofing materials are well-known for their excellent workability and environmental friendliness, but they have a problem that the water evaporation is not performed smoothly and the coating film is easily removed.

Generally, there are two methods of surface treatment of concrete: a method of applying the surface of the concrete with the coating material and a method of penetrating the material into the concrete. By treating the surface of the concrete as described above, penetration of harmful substances such as chlorine ions, moisture, carbon dioxide, etc. outside the concrete is suppressed, thereby reducing the cause of loss of the durability of the concrete structure.

Conventionally, emulsion resins such as polyacrylate emulsion and the like have been mainly used as surface coating agents. Emulsion resin is a type of colloid in which polymer fine particles having a particle size of 200 to 1000 nm are uniformly dispersed in water to form milk, and the state where the fine particles are rubber is referred to as latex and the case where the resin is resin is referred to as an emulsion. An important condition that the above-mentioned emulsion resin should have is the mixing stability with cement. When the emulsion resin is mixed with the cement and kneaded, the emulsion resin is solidified by the mechanical diffusion action or the calcium ions released from the cement so that the emulsion is not broken. However, since conventional products are emulsion-type products made of anionic or nonionic emulsifiers, there is a problem that emulsion particles are large and the stability of particles is caused only by the electrostatic repulsion force, so that the emulsion is easily broken by calcium ions and broken. In addition, in order to impart various physical properties to concrete, conventional products have been required to add various admixtures such as water reducing agents separately.

In relation to concrete surface treatment technology, advanced countries have established strict standards for the content of hazardous substances, and strict regulations are in place to produce only satisfactory products. In Korea, preference for products that mention environment is good And the regulation is also changing strictly, so it is time to develop a product suitable for the trend.

In advanced countries, waterproof coatings are constantly being developed. In Korea, however, simple technical products containing low-cost general coatings or functional materials are being introduced to the market. In the case of high-performance waterproof coatings, In most developed countries, imports at high prices require rapid research and development of environmentally friendly and highly functional special products.

Korea Publication No. 2006-0081071 (published on June 7, 2006)

The present invention is to provide an environmentally friendly, highly functional polymer composite waterproofing agent having an optimum composition and composition ratio that can greatly improve the water resistance and mechanical properties of concrete while using environmentally friendly materials, unlike concrete waterproofing materials that discharge existing harmful substances.

In order to solve the above-described problems, the environmentally friendly high functionality polymer composite waterproofing agent of the present invention can be applied to water, a styrene butadiene rubber (SBR) resin, a vinylacetate ethylene copolymer (VAE) resin, a polymer dispersion, A volatile organic compound (VOC) adsorbent, an antimicrobial preservative, a mecellose, an adhesion strength improving agent, a wear resistance improving agent and an additive.

It is another object of the present invention to provide a concrete structure that is surface-treated using the environmentally friendly high-performance polymer composite waterproofing agent.

The environment-friendly high performance polymer composite waterproofing agent of the present invention minimizes or prevents the emission of TVOC (total volatile organic compound) and heavy metal by introducing an environmentally friendly material as an adsorbent, and has excellent adhesion strength with a concrete paint and / But also has a low water absorption coefficient ratio and is excellent in water resistance, so that the durability stability of the concrete structure can be greatly improved.

Fig. 1 is a XRD measurement graph of the shellfish flow prepared in Preparation Example 1. Fig.
Each of Figs. 2A to 2D shows SEM measurement results of clams, cockles, cockles and oysters, which were measured in Preparation Example 1 in order.
Fig. 3 is a schematic diagram of a test for the formaldehyde and VOC adsorption of the shell powder prepared in Preparation Example 1. Fig.
Fig. 4 shows the results of the adsorption of formaldehyde and VOC (benzene, toluene, xylene) in Preparation Example 1. Fig.
5 shows the result of measurement of the compressive strength of the shell powder measured in Preparation Example 1. Fig.
6 is a photograph of the setting time measured in Experimental Example 2. Fig.
7 is a photograph of the apparatus for measuring compressive strength used in Example 3.
8 is a photograph of a water permeable device used in the water permeability measurement of Experimental Example 5. FIG.
Fig. 9 is a photograph showing a bonding strength test scene of Experimental Example 6. Fig.
10 is a photograph showing a test specimen of stability measurement of Experimental Example 7. Fig.
11A and 11B are photographs showing the acid resistance and alkali resistance of Experimental Example 8, respectively.
12 is a test report obtained by commissioning the measurement of the physical properties of the concrete produced using the mortar of Production Example 1. FIG.
Fig. 13 is a test report submitted for the measurement of acid resistance and alkali resistance of concrete produced using the mortar of Production Example 1. Fig.
Fig. 14 is a test report submitted for TVOC, toluene, and formaldehyde detection measurement of concrete produced using the mortar of Production Example 1. Fig.
Fig. 15 is a test report submitted to the measurement of accelerated weathering resistance of concrete produced using the mortar of Production Example 1. Fig.
16 is a test report requested to measure the freeze-thaw property of concrete produced using the mortar of Production Example 1. Fig.
17A and 17B are test reports submitted to the measurement of heavy metals of the polymer composite waterproofing agent of Example 1. Fig.

Hereinafter, the present invention will be described in more detail.

(Hereinafter referred to as "polymer composite waterproofing agent") of the present invention can be applied to water, a styrene butadiene rubber (SBR) resin, a vinylacetate ethylene copolymer (VAE) resin, a polymer dispersion polymer dispersions, heavy metal-VOC (Volatile organic compound) sorbents, antimicrobial preservatives, mecellose, adhesion strength improvers, abrasion resistance improvers and additives.

The polymer composite waterproofing agent composition of the present invention is low-temperature emulsion polymerization of the above-mentioned SBR resin. The SBR resin is more uniform in quality than the natural rubber resin and has excellent heat resistance and abrasion resistance. In the present invention, the SBR resin improves the abrasion resistance of the concrete paint surface, . The amount of the SBR resin to be used may be 15 to 60 parts by weight, preferably 18.5 to 51 parts by weight, more preferably 25 to 45 parts by weight, based on 100 parts by weight of water. If the amount of the SBR resin is less than 15 parts by weight, the proper compressive strength and adhesion of the surface strengthening agent may not be secured. If the amount of the SBR resin is more than 60 parts by weight, the viscosity of the surface strengthening agent becomes too high, There may be a falling problem.

Among the polymer composite waterproofing composition of the present invention, the VAE resin differs from a general organic adhesive in that it can be adhered to the adherend by simply raising the temperature without using a volatile organic solvent. In the present invention, the amount of the VAE resin may be 8 to 45 parts by weight, preferably 9.2 to 40.8 parts by weight, more preferably 12 to 28 parts by weight based on 100 parts by weight of water. If the amount of the VAE resin used is less than 8 parts by weight, the proper adhesion strength of the surface strengthening agent may not be secured. If the amount of VAE resin is used in excess of 45 parts by weight, it is uneconomical to use excessively, So that there is a problem of lowering the compressive strength. Therefore, it is preferable to use within the above range.

Among the polymer composite waterproofing agent compositions of the present invention, the polymer dispersions serve to improve resistance to moisture permeation and absorption of the surface strengthening agent, and those commonly used in the art can be used, and preferably, vinyl acetate- Vinyl acetate copolymers, styrene-butadiene copolymers, vinyl acetate copolymers, vinyl acetate copolymers, vinyl acetate copolymers, ethylene-vinyl acetate copolymers and styrene- Can be used in combination. In the present invention, the amount of the polymer dispersions may be 4 to 24 parts by weight, preferably 4.8 to 20.4 parts by weight, more preferably 6 to 18 parts by weight, based on 100 parts by weight of water, If the amount of the purging agent is less than 4 parts by weight, the amount of the purging agent used may be too small to increase the water absorption coefficient of the surface strengthening agent. When the amount of the purging agent is more than 24 parts by weight, compatibility and miscibility And the overall mechanical properties of the surface strengthening agent may be deteriorated. Therefore, it is preferable to use within the above range.

In addition, the heavy metal-VOC adsorbent in the composition of the polymer composite waterproofing agent of the present invention plays a role of preventing and / or minimizing the release of heavy metals and volatile organic compounds generated in concrete structures, concrete paints, etc. to the outside of the concrete structure. As the heavy metal-VOC adsorbent in the present invention, a shell powder, which is an eco-friendly material, may be used. Preferably, the heavy metal-VOC adsorbent may be a mixture of two or more species selected from among shellfish shellfish, clam shellfish shellfish and clam shellfish shell, Is advantageous in terms of cost competitiveness and material water acuity. The shell powder is preferably pulverized to have an average particle diameter of 15 mu m to 40 mu m. In the present invention, the amount of the heavy metal-VOC adsorbent to be used is preferably 6 to 15 parts by weight, preferably 7.2 to 10.3 parts by weight, more preferably 8 to 10 parts by weight, based on 100 parts by weight of water. If the amount of the heavy metal-VOC adsorbent used is less than 6 parts by weight, the amount of the heavy metal and VOC adsorbent may be too small to cause a heavy metal and / or VOC adsorption effect It is preferable to use within the above range.

The antimicrobial preservative of the polymer composite waterproofing composition of the present invention is used for imparting antimicrobial and / or antifungal functions, and may be any of those generally used in the art. Preferably, the antimicrobial preservative is selected from the group consisting of kaolin, Two or more of them may be used in combination, and more preferably, kaolin may be used. The antimicrobial preservative may be used in an amount of 2 to 10 parts by weight, preferably 3.5 to 8.3 parts by weight, more preferably 5 to 8 parts by weight. If the antimicrobial preservative is used in an amount of less than 2 parts by weight, The antimicrobial effect can not be obtained because the amount is too small, and it is uneconomical to use more than 10 parts by weight.

Also, among the polymer composite waterproofing agent compositions of the present invention, the above-mentioned mecellose is a water-soluble polymer prepared by replacing hydroxyl groups in cellulose molecules with methoxy groups and hydroxypropyl groups through etherification reaction. In the present invention, . The amount of the mecellose used in the present invention is preferably 0.5 to 5 parts by weight, preferably 1.2 to 2.2 parts by weight, more preferably 1.5 to 2 parts by weight, based on 100 parts by weight of water. If the amount is more than 5 parts by weight, the viscosity may excessively increase, causing problems in use of the product. Therefore, the amount of the component used within the above range It is good.

Also, the adhesion strength improver of the polymer composite waterproofing composition of the present invention can improve the initial coating workability of the surface strengthening agent, the adhesion property with the concrete surface and / or the concrete paint or the like by filling the voids through the chemical reaction, , Thereby improving the adhesion strength. The adhesion strength improving agent may be a mixture of two or more species selected from among sodium silicate and calcium formate, preferably sodium silicate. In the present invention, the amount of the adhesion strength improving agent used is preferably 1 to 7 parts by weight, preferably 1.5 to 6.1 parts by weight, more preferably 2 to 5 parts by weight, based on 100 parts by weight of water, If the amount is less than 1 part by weight, it may not be possible to obtain an appropriate improvement in the adhesion strength. If the amount of the adhesion-improving agent is more than 7 parts by weight, It is good to use.

In addition, the abrasion resistance improver of the polymer composite waterproofing composition of the present invention has a function of improving the surface strength, increasing the abrasion resistance, and increasing the heat resistance of the surface strengthening agent. Carbon black is preferably used as the abrasion resistance improving agent. In the present invention, the abrasion resistance improver is used in an amount of 1 to 5 parts by weight, preferably 1.2 to 2.5 parts by weight, more preferably 1.5 to 2.3 parts by weight based on 100 parts by weight of water. If the amount of the abrasion resistance improver used is less than 1 part by weight, the amount of the abrasion resistance improver used may be too small to improve the abrasion resistance and surface strength. If the abrasion resistance improver is used in excess of 5 parts by weight, Therefore, it is preferable to use within the above range.

The polymer composite waterproofing agent of the present invention may further comprise at least one additive selected from a defoaming agent, a dispersing agent and a plasticizer. The amount of the additive to be used is 0.1 to 10 parts by weight, preferably 0.6 to 1.8 parts by weight It is recommended to use it in the sub range.

The antifoaming agent among the additives may be selected from those commonly used in the art. Preferably, the antifoaming agents may be used alone or in combination of two or more selected from mineral oil type, silicone type and non-silicone type polymers.

The above-mentioned dispersants among the additives may be those generally used in the art, and may be used alone or in admixture of two or more selected from among water dispersants.

Among the additives, the plasticizers commonly used in the art can be used. Preferably, the plasticizer is selected from a phthalate ester plasticizer, a straight chain dibasic acid ester plasticizer, a computed ester plasticizer, a polyester plasticizer and a nitrile synthetic rubber. Or two or more of them may be used in combination.

The surface strengthening agent of the present invention composed of the composition and composition ratio described above may have an adhesion strength of 2.00 N / mm ² or more, preferably 2.03 to 2.15 N / mm ² when measured according to KS F 4925.

The polymer composite waterproofing agent of the present invention may have a compressive strength of 31.0 N / mm ² or more, preferably 32.0 to 35.0 N / mm ² , more preferably 32.5 to 34.8 N / mm ² , as measured according to KS F 4925. mm can be ^two days.

In addition, the polymer composite waterproofing agent of the present invention may have a water absorption coefficient ratio of 0.29 or less, preferably 0.250 to 0.285, as measured according to KS F 2609.

The polymer composite waterproofing agent of the present invention may have an adhesive strength of 0.6 N / mm ^{2 or} more after freeze-thaw dissolution when measured according to KS F 4925, preferably 0.65 to 1.0 N / mm ² Lt; / RTI >

The polymer composite waterproofing agent of the present invention may have a total volatile organic compound (TVOC) emission of 0.004 mg / (m ² · h) or less, preferably 0.001 to 0.0035 mg / (m ² · h) h).

The polymer composite waterproofing agent of the present invention may have a formaldehyde emission of 0.03 mg / (m ² · h) or less, preferably 0.001 to 0.025 mg / (m ² · h) ).

Further, the polymer composite waterproofing agent of the present invention is excellent in durability stability and has no expansion, crack or twist, and is excellent in acid resistance and alkali resistance, so that it is a surface strengthening agent having no or minimal cracking, peeling, and leaching. In addition, it has excellent weatherability and freezing solubility.

By coating the polymer composite waterproofing agent of the present invention on the surface of the concrete and / or the concrete paint, excellent durability, waterproofness, mechanical strength and environmentally friendly concrete structure can be provided.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

[ Example ]

Preparation Example  1: Heavy metal - VOC  Adsorbent selection

The basic physical properties of shells such as specific gravity measurement and chemical composition analysis were measured for four representative shells (oysters, clams, clams, clams) produced in Korea, and after the crushed shells were mixed into cement mortar, The optimum shell powder was selected by evaluating applicability to the paint surface strengthening agent.

(1) Measurement of specific gravity and absorption rate of moisture

The specific gravity (KSM0602) and the water uptake rate (KSF2504) were measured to confirm the physical performance of the shellfish.

The specific gravity of the shellfish and the water absorption rate to moisture are shown in Table 1. The specific gravity of the shell except for oysters was measured in the range of 2.6 to 2.7 g / cm 3, and the absorption rate was 1.8 to 2.0% Respectively. On the other hand, in the case of oysters, the specific gravity was measured to be 1.358 g / ㎤ which is half of the other shells and the absorption rate was 9.4%, which is higher than other shells. Taken together, it is considered that the oysters are made of porous materials that are relatively weaker than shells of cockles, clams, and clams.

division oyster Squirrel clam Clam Test Methods Specific gravity (g / cm3) 1.358 2.743 2.690 2.697 KS M 0602 Absorption Rate (%) 9.44 2.02 1.85 2.48 KS F 2504

(2) X-ray fluorescence analyzer XRF ) Measure

The chemical components of the shellfish were analyzed using XRF, and the results are shown in Table 2. The measured data are shown in FIGS. 1A and 1B. In all shells except oysters, CaO content was found to be over 90%, and other contents of SiO ₂ and Na ₂ O were found.

In the case of oysters, CaO content was measured to be high, but it was about 10% lower than other shells. In addition, unlike other shells, oysters contained 5.9% Cl components.

division CaO Na ₂ O SiO ₂ SO ₃ Al ₂ O ₃ Fe ₂ O ₃ P ₂ O ₅ K ₂ O Clam 94.9734 1.0125 1.8393 0.5283 0.4542 0.5815 0.1260 0.0939 Squirrel 95.9515 - 1.6848 0.6587 0.5836 0.5905 0.1003 0.0807 clam 92.7901 1.1309 3.0987 0.5925 0.9850 0.6332 0.2282 0.1327 oyster 84.5974 5.9262 1.6319 1.1921 0.4529 0.3224 0.2947 0.2390

The analysis of the XRD data in FIG. 1 reveals that Aragonite and Calcite are composed of CaCO ₃ in the case of clams, cockles and clams, but most of them are composed of aragonite . On the other hand, oysters consist mostly of calcite, and some quartz and sodium chloride (NaCl) are also contained.

Considering the overall data, the chemical composition of the actual shell is the same as CaCO ₃ , and it can be seen that only the crystal structure differs in the form of aragonite or calcite.

(3) SEM  Measure

SEM measurement was performed to confirm the shape structure of the inner and outer surfaces of the shell, and the results are shown in Figs. 2A to 2D. Fig. 2 (a) is a barnacle, Fig. 2 (b) is a cross section, Fig. 2 (c) is a cross section and Fig. 2 (d) is a SEM measurement result.

2d, the inner and outer shapes of the oysters were observed to be a plate-like laminate structure, and it was confirmed that the thin lamina-like layers were superimposed on the layers. 2c, the outer shape of the mating was also observed in a plate-like laminate structure similar to oyster. However, it can be seen that the laminated layer is thicker than the oyster, which is closely related to the strength of the shell itself.

On the other hand, in the case of the clods and clumps of Figs. 2B and 2A, the crystal structure is composed of aragonite as in the case of clay, but no lamellar structure like a clay was observed, and no specificity on the microstructure was observed.

(4) Of shell powder Formaldehyde  And VOC  Adsorption test

The adsorption characteristics of the volatile organic compounds represented by formaldehyde and benzene were measured by exposing the volatile organic compounds such as formaldehyde and benzene in the adsorption chamber.

The test specimens containing 0%, 10%, 30% and 50% of shellfish powder were exposed to formaldehyde and VOC (benzene, toluene, xylene) at high concentration of 27.7 ~ 28.5㎎ / . A schematic diagram of the adsorption force test is shown in Fig. 3 to facilitate understanding.

4 shows results of the adsorption force measurement, wherein (a) is a formaldehyde, (b) is benzene, (c) is toluene, and (d) is a measurement result of xylene adsorption amount.

As shown in FIG. 4, it can be confirmed that the larger the content of the shell powder is, the more the adsorbability increases.

(5) Of shell powder  Compressive strength measurement

Cement mortar was prepared by mixing 20% of the shell powder of four kinds (shellfish, clams, clams, oysters) with respect to the weight of fine aggregate, and the compressive strength was tested for 7 days according to the KS L ISO 679 test method. .

The compressive strength of Plain was measured at 14.1 MPa for 7 days, and 13.29 MPa, 11.50 MPa, and 13.35 MPa were measured for each case of cockroach, clam, and clam. It can be seen that the inclusion of shellfish generally results in the reduction of compressive strength.

However, in the case of cement mortar mixed with clods and clams, the standard deviation of compressive strength was close to the deviation range of the plain.

On the other hand, the compressive strength of the mortar containing oyster shell was 9.08 MPa, which was about 35% lower than the plain strength.

Taking into consideration the above physical and chemical test results, it is suitable to use as a heavy metal-VOC adsorbent, except for oysters. In consideration of price competitiveness and material water acuity, - VOC adsorbent.

Example  One : Shell  Eco-friendly high functionality using powder Polymer  Manufacture of composite waterproofing agent

34.8 parts by weight of polystyrene-butadiene rubber (SBR) resin, 25 parts by weight of a vinyl acetate ethylene copolymer (VAE) resin, 100 parts by weight of a vinyl disulfide-vinyl acetate-versatile liquid vinyl ester copolymer (VINNAPAS EP701) 1.2 parts by weight of a shellfish shell powder having an average particle diameter of 15 to 40 占 퐉 as a heavy metal-VOC adsorbent, 5.9 parts by weight of kaolin as antimicrobial preservative, 1.7 parts by weight of mecellose, 3.8 parts by weight of sodium silicate as an adhesion strength improving agent, , 1.85 parts by weight of carbon black, 0.5 part by weight of NOPCO NXZ (antifoaming agent), 0.3 part by weight of SNDISPERSANT 44S (dispersant) and 0.5 part by weight of a plasticizer were mixed and stirred to prepare an eco-friendly functional concrete surface strengthening agent.

Example  2 ~ Example  3 and Comparative Example  1 ~ Comparative Example  3

Examples 2 to 3 and Comparative Examples 1 to 3 were each prepared by preparing surface-strengthening agents having the composition ratios shown in Table 3 below, in the same manner as in Example 1, except that the surface-strengthening agents for environmentally functional concrete coatings were prepared.

division
(Parts by weight) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 water 100 100 100 100 100 100 SBR resin 34.8 35.7 28.5 34.8 33.5 63 VAE resin 25 15.3 27.2 25 50 25 Polymer
Dispersion 12.6 15.2 10.9 2.0 5.0 12.6 Heavy metal-VOC adsorbent 1.2 1.2 1.2 1.2 1.2 1.2 Antimicrobial activity
antiseptic 5.9 5.9 5.9 5.9 5.9 Messelos 1.7 1.7 1.7 1.7 1.7 0.3 Bond strength
Enhancer 3.8 3.8 3.8 3.8 3.8 3.8 Abrasion resistance
Enhancer 1.85 1.85 1.85 1.85 1.85 1.85 Defoamer 0.5 0.5 0.5 0.5 0.5 0.5 Dispersant 0.3 0.3 0.3 0.3 0.3 0.3 Plasticizer 0.5 0.5 0.5 0.5 0.5 0.5

Experimental Example  1: Heavy metal detection measurement

In order to verify the toxicity test, four major heavy metals such as hexavalent chromium, lead, cadmium, and mercury, which are hazardous substances due to the polymer components in the polymer composite waterproofing agents of Examples 1 to 3, .

Four heavy metals were prepared by dissolving the heavy metals in the test solution, and the lead spectral light source was attached to the spectrometer and the conditions for lead determination were set. The absorbance of hydrochloric acid was first measured with a spectrophotometer, and the absorbance of the test solution was measured to calculate the content of harmful substances.

Lead and cadmium were measured according to IEC 62321 Ed.1: 2008 (ICP), mercury was measured according to IEC 62321 Ed.1: 2008 (CV-AAS), hexavalent chromium was measured according to IEC 62321 Ed.1: 2008 (UV / VIS), and the results are shown in Table 4 below. The heavy metal detection test report of the polymer composite waterproofing agent of Example 1 is shown in Figs. 17A and 17B.

division Pb (mg / kg) Cd (mg / kg) Hg (mg / kg) Cr ^{6 +} (mg / kg) Example 1 Not detected Not detected Not detected Not detected Example 2 Not detected Not detected Not detected Not detected Example 3 Not detected Not detected Not detected Not detected

Manufacturing example  1 ~ Manufacturing example  3 and Comparative Manufacturing Example  1 ~ Comparative Manufacturing Example  3

The polymer composite waterproofing agents of Examples 1 to 3 and Comparative Examples 1 to 3 were mixed with ordinary Portland cement and silica sand at a weight ratio of 1: 2 to prepare a mixture. Then, the mixture and water were mixed at a weight ratio of 1: 0.5 Cement mortar were sequentially prepared as shown in Table 5 below.

division Polymer composite waterproofing agent Production Example 1 Example 1 Production Example 2 Example 2 Production Example 3 Example 3 Comparative Preparation Example 1 Comparative Example 1 Comparative Production Example 2 Comparative Example 2 Comparative Production Example 3 Comparative Example 3

Experimental Example  2: Measurement of condensation time

Using a cement mortar of each of Production Example and Comparative Production Example, a bottom surface diameter of about 7.5 cm, a top surface diameter of about 5.0 cm, and a center surface thickness of about 1.3 cm were formed on a clean glass plate having a square of about 10 cm, .

The coagulation time was measured using a Gilmor apparatus according to KS F 4925: 2011. To measure the coagulation time, the needle was placed in a vertical position and lightly applied to the surface of the pad. Then, the pad was gilted The cement was terminated when it was supported by acupuncture, while the cement was terminated when the acupuncture point was supported (see FIG. 6). The results are shown in Table 6 below.

division result ( Hours: Minutes ) Production Example 1 Fresh 4:55 closing 7:40 Production Example 2 Fresh 5:00 closing 7:55 Production Example 3 Fresh 4:40 closing 7:50 Comparative Preparation Example 1 Fresh 4:10 closing 6:30 Comparative Production Example 2 Fresh 4:13 closing 7:50 Comparative Production Example 3 Fresh 4:15 closing 7:10

As a result of the measurement in Table 6, it was confirmed that the evaporation of water was delayed and the condensation proceeded stably as compared with the comparative example.

Experimental Example  3: Compressive strength measurement

Production Examples 1 to 3 and Comparative Production Examples 1 to 3 were made to have a floor value of 100 to 115 mm according to 9 of KS L 5105 by using a flow table and a float of KS L 5105 3.6.

Subsequently, mortar with a floor matched to a molding frame (50 mm x 50 mm x 50 mm) was poured, and immediately after being cured for 48 hours in a humid condition of temperature (20 3) Cured in a humid place.

After that, it was stored for 7 days under the standard condition of temperature (20 ± 3) ℃ and humidity (60 ± 5)%, and the compressive strength was measured according to KS F 4925 test method. The compressive strength measurement equation is shown in the following Equation 1, and the results are shown in Table 7, and a compressive strength measurement photograph is shown in FIG.

[Formula 1]

T in Equation 1 is the maximum compression load (N) value.

division Compressive strength (N / mm2) Production Example 1 32.1 Production Example 2 34.6 Production Example 3 32.1 Comparative Preparation Example 1 26.5 Comparative Production Example 2 28.2 Comparative Production Example 3 29.4

Experimental Example  4: Measurement of water absorption coefficient

The water absorption coefficient was measured by using specimens of φ150 mm × 40 mm in accordance with KS F 2609 (Method of measuring water absorption coefficient of building materials) of specimens prepared from the mortar of Production Examples 1 to 3 and Comparative Production Examples 1 to 3 After drying for 48 hours at temperature (80 ± 2) ℃, the side surface is waterproofed with paraffin and epoxy. Then, if paraffin and epoxy are cured, the initial weight is measured and immersed in water at about 20 ° C to a depth of 2 to 10 mm . Next, the weight of the specimen is measured at intervals of a predetermined time. At this time, the water on the surface is removed by using a wet cloth and measured. The water absorption coefficient was calculated by the following equation (2).

[Formula 2]

In Equation 2

(G), and t is time (sec).

The water absorption coefficient ratios were measured according to the following formula 2, and the results are shown in Table 8 below.

[Formula 3]

Coefficient of water absorption ratio = {a surface coefficient of water absorption of the mortar specimen with enhancer (kg / m ² and ^0.5 h)) / {Coefficient of water absorption of the mortar specimen unused surface reinforcing agent (kg / m ² and ^0.5 h))

division Water absorption coefficient ratio Production Example 1 0.28 Production Example 2 0.29 Production Example 3 0.32 Comparative Preparation Example 1 0.43 Comparative Production Example 2 0.36 Comparative Production Example 3 0.39

Experimental Example  5: Measurement of permeability

After putting each of the mortars of the production example and the comparative production example into a mold (ø150 mm × 40 mm), the mortar was immediately dried for 5 days under the standard condition of temperature (20 ± 3) ° C. and humidity (60 ± 5)%. After that, the test specimens were lightly brushed at the center part of the diameter of 50 mm or more on both sides thereof to remove the latices and demolders, dried at 80 ° C. for 24 hours and then waterproofed with paraffin or quick hard epoxy resin, 3) 占 폚 and humidity (60 占)%.

After the mass of the specimen was measured, the specimen to which the hydraulic pressure was applied was taken out of the permeability testing apparatus, and the water on the surface was removed by using a wet cloth and then the mass was measured.

The permeability test was conducted by measuring the permeability of five test specimens mixed with five surface-strengthening agents and five specimens not mixed with each other, 4, the permeability ratio was calculated. The permeation equipment is shown in Fig.

[Formula 4]

In the formula (4), W _p is the water permeability (g), W ₁ is the mass after drying (g) and W ₂ is the mass after permeation (g).

division Pitch ratio Production Example 1 0.36 Production Example 2 0.39 Production Example 3 0.36 Comparative Preparation Example 1 0.41 Comparative Production Example 2 0.38 Comparative Production Example 3 0.40

Experimental Example  6: Bond strength measurement

A test specimen prepared by placing and curing each of the mortars of the production example and the comparative production example was placed horizontally in a test chamber on a molding frame (40 mm x 40 mm x 5 mm), the adhesive was applied to the sample application surface, (Made of steel) was gently put on it, gently rubbed and adhered thereto, and then a weight of 1 kg was placed thereon to carefully remove the adhesive that had been spilled around. The weight was removed for 24 hours, and the maximum tensile load was measured by applying a tensile force in a direction perpendicular to the sample surface using a tensile jig (made of steel) and a steel plate.

The bond strength was measured with five test pieces according to the following equation (5), and the highest and lowest values were discarded, and the remaining three measured values were averaged. A photograph of the measurement test thereof is shown in Fig.

[Formula 5]

In Equation 5, T is the maximum tensile load (N).

division Bond strength (N / mm2) Production Example 1 2.07 Production Example 2 2.00 Production Example 3 2.10 Comparative Preparation Example 1 1.68 Comparative Production Example 2 1.45 Comparative Production Example 3 1.60

Experimental Example  7: Stability (durability) test

The mortar of Preparation Example and Comparative Preparation Example was placed on a glass plate having a width of about 130 mm and a length of about 130 mm, and rubbed lightly from the edge with a spatula into a circular shape having a diameter of about 100 mm. . Next, the sample was put into a moisture chamber immediately after the preparation and cured for about 24 hours. At this time, if the temperature in the moisture chamber should be maintained at (20 ± 3) ° C, the humidity was set to 80% or more, and the water temperature of the water tank for immersing the test body was (20 ± 3) ° C.

At this time, two immersed samples were stored in a humid chamber for about 24 hours and then placed in a water tank for 27 days to check for inflatable cracks or twists.

Fig. 10 shows the photographs of the test specimens measured for stability, and the results are shown in Table 11 below. The stability test is based on KS F 4925: 2011.

division Stability test Production Example 1 clear Production Example 2 clear Production Example 3 clear Comparative Preparation Example 1 clear Comparative Production Example 2 clear Comparative Production Example 3 clear

12 shows a test report submitted to a test such as the compressive strength, the stability and the water absorption coefficient ratio of the test piece of Production Example 1. [

Experimental Example  8 : Acid resistance , Alkali resistance  Measure

(One) Acid resistance  Measure

Each of the mortars of Preparation Example and Comparative Preparation Example was applied twice at intervals of 24 hours at a height of 70 mm × 70 mm × 10 mm and allowed to stand for 24 hours. The periphery of the test piece was overlapped with the coating film by about 5 mm or more And allowed to stand for 6 days.

The periphery of the test plate was immersed in the melted paraffin (melting point 55 ° C to 65 ° C) in order, and allowed to stand for 1 hour in such a manner that the thickness of the first test piece was about 3 mm and that of the second test piece was about 5 mm. I dipped for three hours. The acid resistance was measured by the presence of cracks, peeling, peeling, elution and the like in two or more pieces of three test pieces.

(2) Alkali resistance  Measure

Each of the mortars of Preparation Example and Comparative Preparation Example was applied twice at intervals of 24 hours at a height of 70 mm × 70 mm × 10 mm and allowed to stand for 24 hours. The periphery of the test piece was overlapped with the coating film by about 5 mm or more And allowed to stand for 6 days.

The periphery of the test plate was immersed in the paraffin (melting point 55 ° C to 65 ° C), which was melted in order, and the solution was allowed to stand for 1 hour in such a manner that the thickness of the first test piece was about 3 mm and that of the second test piece was about 5 mm. For 3 hours. Alkali resistance was measured in two or more pieces of three test pieces in terms of cracks, peeling, peeling, elution and the like.

The measurement results are shown in Table 12, and the acid resistance measurement photographs of Production Example 1 are shown in FIG. 11A and the alkyl resistance measurement results for Production Example 1 are shown in FIG. 11B. The acid resistance and alkali resistance are measured according to KS M 6030: 2014.

The results of the acid resistance and alkali resistance test for Production Example 1 are shown in Fig.

division Acid resistance Alkali resistance Production Example 1 clear. clear. Production Example 2 clear. clear. Production Example 3 clear. clear. Comparative Preparation Example 1 Poured on the psalm clear Comparative Production Example 2 Pitted on specimen clear Comparative Production Example 3 clear clear

Experimental Example  9: TVOC  And toluene, Formaldehyde  Detection test

The TVOC (total volatile organic compound) emission amount and toluene, formaldehyde emission amount measurement of Example 1 were tested in accordance with the indoor air quality process test standard according to Ministry of Notification No. 2010-4.

The test conditions of the small chamber used for the measurement are shown in Table 13, and the measurement conditions of the total volatile organic compound and toluene are shown in Table 14, and the conditions for measuring the formaldehyde are shown in Table 15 below.

FIG. 14 shows TVOC, toluene and formaldehyde detection test results for Production Example 1. FIG.

Sample form Liquid building material Sample classification glue Amount of sample 302 g / ㎡ Sample loading rate 0.4 m 2 / m 3 Temperature 24.0 to 26.0 Number of ventilation 0.50 times / h Relative humidity 47% to 54%

Test Items unit result TVOC mg / (m < 2 > h) 0.004 Toluene mg / (m < 2 > h) Not detected Formaldehyde
(Formaldehyde) mg / (m < 2 > h) 0.023

According to the measurement results of Table 16, toluene was not detected at all and only trace amounts of TVOC and formaldehyde were generated.

Experimental Example  10: Accelerated weathering test

Preparation Examples and Comparative Preparations The test pieces were prepared in accordance with KS F 2274: 2002, and the accelerated weathering resistance was measured under the conditions shown in Table 17 below. The results are shown in Table 18 below.

More specifically, the test was carried out in the following order in accordance with the exposure conditions of the Sunshine Carbon Arc. The carbon was mounted on the upper carbon holder and the lower carbon holder of the lamp, and then the cleaned filter was attached without pollution and breakage. Next, a black panel thermometer for measurement was mounted on a drum or a frame, the test piece was put into a sample holder, mounted on a drum or a frame, and a sample holder was attached to a drum or a frame portion on which the test piece was not mounted. Then, the time switch was set at a predetermined time, the rotation was started, the discharge current voltage was adjusted, and it was confirmed that the black panel thermometer was 63 3 C when the temperature in the tester was stable. Then, the spray cycle was set, and it was confirmed whether the sample spray spray was normal, and the operation was repeatedly measured until reaching the predetermined time.

The accelerated weatherability test report of Production Example 1 is shown in Fig.

Item Exposure test method WS -A Carbon arc voltage / current AC voltage tolerance range 48 ~ 52V, center value 50 ± 1V
AC current allowable range 58 ~ 62A, center value 60 ± 1.2A filter Type Ⅰ or Ⅱ Radiation intensity of the surface of specimen 225 占 (10%) W / m2 (wavelength range 300 to 700 nm) Black panel temperature 63 ± 3 Relative humidity (50 ± 5)% On the specimen surface
Water spray cycle After 102 minutes irradiation, 18 minutes irradiation and water spraying, or 48 minutes irradiation and 12 minutes irradiation and water spraying Investigation method Continuous investigation

division Appearance after accelerated weathering test (swelling, cracking, falling) Production Example 1 clear Production Example 2 clear Production Example 3 clear Comparative Preparation Example 1 clear Comparative Production Example 2 Separated from the concrete matrix Comparative Production Example 3 Separated from the concrete matrix

Experimental Example  11: Freezing and thawing test

Preparation Examples and Comparative Preparations After preparing test pieces with mortar, the resistance to freezing and thawing of the developed product against rapid freezing and thawing of KS F 2456 and the adhesion strength after long term melting according to KS F 4925 were measured. This is a method for quantitatively predicting the service life of the concrete structure against the durability of the concrete, and is intended to evaluate the durability of the developed product.

After the curing period was over, the specimen was moved to the state of (6 ± 3) ℃ to measure the first resonance frequency and mass of the deformation vibration. The specimen was kept at a constant temperature from the end of curing until the beginning of the freezing and thawing cycle Respectively.

At the beginning of the frozen state during the cycle, the specimen is placed in the melt and the freezing and thawing test is started. The test was ended at 100 cycles. When there was a cycle in which the relative dynamic modulus was 60% or less, the test was completed in that cycle.

The freeze / thaw test result of Production Example 1 is shown in Fig.

division After freezing and thawing, After freeze-thaw,
Bond strength (N / mm2) Production Example 1 clear. 0.7 Production Example 2 clear. 0.8 Production Example 3 clear. 0.8 Comparative Preparation Example 1 Gap generated 0.2 Comparative Production Example 2 Peeled 0 Comparative Production Example 3 Peeled 0

The polymer composite waterproofing agent of the present invention can minimize or prevent TVOC (Total Volatile Organic Compound) and heavy metal emissions while using environmentally friendly materials, and can provide excellent adhesion to concrete paint and / or concrete surface Strength and compressive strength as well as a water absorption coefficient with a low water absorption coefficient ratio. Thus, it can be confirmed that the durability stability of the concrete structure can be greatly improved.

Claims (10)

delete delete delete delete delete 25 to 45 parts by weight of a styrene butadiene rubber (SBR) resin, 12 to 28 parts by weight of a vinylacetate ethylene copolymer (VAE) resin, 6 to 18 parts by weight of a polymer dispersion 6 to 15 parts by weight of a heavy metal-VOC (Volatile organic compound) adsorbent, 0.5 to 5 parts by weight of mecellose, 2 to 10 parts by weight of an antimicrobial preservative, 1 to 7 parts by weight of an adhesion strength improving agent, And 0.1 to 10 parts by weight of an additive,
The polymer dispersion may be selected from the group consisting of vinyl acetate and vinyl ester of Versatic Acid copolymer, ethylene-vinyl acetate copolymer and styrene-butadiene copolymer. copolymers, and the like.
Wherein the heavy metal-VOC adsorbent comprises a shell powder obtained by pulverizing shell shells containing at least one selected from the group consisting of a shell shell, a shell shell, and a shellfish shell shell,
Wherein the antimicrobial preservative comprises at least one selected from kaolin and an industrial preservative,
Wherein the adhesion strength improving agent comprises at least one selected from the group consisting of sodium silicate and calcium formate,
Wherein the abrasion resistance improver comprises carbon black,
The additive includes at least one selected from a defoaming agent, a dispersant, and a plasticizer,
KS F 4925, the adhesive strength is not less than 2.00 N / mm ² and the compressive strength is not less than 31.0 N / mm ² ,
(TVOC) emissions of less than 0.004 mg / (m ² · h) and formaldehyde emissions of 0.03 mg / (m ² · h) when measured according to the Ministry of the Environment Notice No. 2010-4 h) or less, based on the total weight of the water-soluble polymer. The method according to claim 6,
Characterized by having a water absorption coefficient ratio of 0.29 or less when measured according to KS F 2609. 2. The waterproofing agent for concrete according to claim 1, delete delete A concrete structure comprising the environmentally-friendly high-functional polymer composite waterproofing agent of claim 6 or 7.

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