KR102337094B1 - Polymer modified ultra rapid hardening cement concrete compositions having high strength and high durability and repairing method of road pavement using the same - Google Patents

Abstract

The present invention relates to a polymer-modified ultra-fast hardening cement concrete composition with high strength and durability, and a road repairing method using the same. More specifically, the polymer-modified ultra-fast hardening cement concrete composition comprises 5 to 50 wt% of fine aggregate, 5 to 40 wt% of coarse aggregate, 0.1 to 10 wt% of water, 5 to 40 wt% of an ultra-fast hardening cement binder, and 1 to 30 wt% of a polymer modifier. The ultra-fast hardening cement binder includes 100 parts by weight of rapid hardening Portland cement, 20 to 40 parts by weight of calcium sulfoaluminate, 1 to 20 parts by weight of ground calcium carbonate, 1 to 20 parts by weight of electric furnace reduced slag, 1 to 20 parts by weight of titanium carbonitride, 1 to 20 parts by weight of alkali silicate, 0.1 to 10 parts by weight of graphite, and 0.1 to 10 parts by weight of magnesium fluoride. The polymer modifier includes 100 parts by weight of styrene-methyl methacrylate-butadiene copolymer, 70 to 90 parts by weight of ethylene-glycidyl methacrylate copolymer, 10 to 30 parts by weight of acetoacetoxyethyl methacrylate, 10 to 30 parts by weight of diacetone acrylamide parts by weight, 0.1 to 10 parts by weight of polyrotaxane, and 0.1 to 10 parts by weight of polyglycerol-polyglycidyl ether. According to the present invention, strength is stably expressed and high-strength characteristics are expressed in an early stage, thereby minimizing a traffic control period and providing excellent resistance to freeze-thaw, neutralization and salt damage.

Description

Polymer modified ultra rapid hardening cement concrete compositions having high strength and high durability and repairing method of road pavement using the same}

The present invention can minimize the traffic control period by enabling stable strength expression as well as early expression of high strength characteristics; The present invention relates to a polymer-modified super-fast cement concrete composition having high strength and high durability, which is also excellent in resistance to freeze-thaw, neutralization and salt damage, and to a road repair construction method using the same.

Recently, the problem of durability of concrete structures has emerged as a social problem. In particular, the problem of durability deterioration due to salt damage, carbonation, alkali aggregate reaction, corrosion of reinforcing bars and destruction of concrete, and the problem of deterioration of safety due to exfoliation or earthquakes have been widely discussed. In particular, environmental pollution is becoming increasingly serious with the rapid progress of modernization and industrialization in our society, and the acidification of the atmosphere and acid rain accelerate the deterioration of concrete due to the increase in carbon dioxide and sulfur dioxide, which are harmful substances that corrode concrete. are making

Roads are generally paved with asphalt or concrete and constructed. In particular, road gutters are provided at the edge of the road to drain water accumulated on the road. These roads have a problem in that aging and deterioration become more severe over time due to direct impact by vehicles, freezing and thawing in winter, and salt damage such as calcium chloride. In addition, when these roads are exposed for a long time in an ultra-high or ultra-low temperature state, they contract and expand by a greater width than the design amount according to a change in external temperature. In severe cases, the length change stress is excessively generated, resulting in cracks due to elevation, subsidence or torsion between the concrete separation plates, resulting in severe damage to the structure and pavement and deterioration of durability.

Such deteriorated or damaged roads require periodic maintenance to ensure long-term usability. In order to be able to construct it, a super-velocity material should be used.

In order to manufacture such a super-velocity material, Korean Patent Registration Nos. 10-1665945 and 10-2133439 disclose various super-velocity materials for repairing and reinforcing damaged parts of roads.

However, in the case of the conventional super-velocity material, although the material cost is increased due to the addition of polymer, the expected effect on strength and durability is low, so there is a disadvantage that the effect of reducing the maintenance cost is insignificant.

Republic of Korea Patent Registration No. 10-1665945 Republic of Korea Patent No. 10-2133439

The present invention has been devised to solve the above-described problems, and an embodiment of the present invention enables stable strength expression, as well as high strength characteristics such as compressive strength, flexural strength, and adhesive strength, to be expressed at an early stage, thereby minimizing the traffic control period. there is; An object of the present invention is to provide a polymer-modified super-fast cement concrete composition having high strength and high durability with excellent durability due to excellent resistance to freeze-thaw, neutralization and salt damage.

In addition, another embodiment of the present invention is to provide a road repair construction method using the polymer-modified super-fast cement concrete composition having high strength and high durability.

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

An embodiment of the present invention comprises 5 to 50% by weight of fine aggregate, 5 to 40% by weight of coarse aggregate, 0.1 to 10% by weight of water, 5 to 40% by weight of a super fast cement binder, and 1 to 30% by weight of a polymer modifier. A polymer-modified super-fast cement concrete composition having high strength and high durability;

The super fast cement binder is 100 parts by weight of crude Portland cement, 20 to 40 parts by weight of calcium sulfoaluminate, 1 to 20 parts by weight of heavy calcium carbonate, 1 to 20 parts by weight of electric furnace reduced slag, 1 to 20 parts by weight of titanium carbonitride , 1 to 20 parts by weight of alkali silicate, 0.1 to 10 parts by weight of graphite, and 0.1 to 10 parts by weight of magnesium fluoride;

The polymer modifier is styrene-methyl methacrylate-butadiene copolymer 100 parts by weight, ethylene-glycidyl methacrylate copolymer 70 to 90 parts by weight, acetoacetoxyethyl methacrylate 10 to 30 parts by weight, diacetone acrylic It provides a polymer-modified super-fast cement concrete composition having high strength and high durability, containing 10 to 30 parts by weight of amide, 0.1 to 10 parts by weight of polyrotaxane, and 0.1 to 10 parts by weight of polyglycerol-polyglycidyl ether.

The titanium carbonitride is a step of preparing a mixture of titanium oxide (TiO ₂ ) powder and expanded graphite, pulverizing the mixture, and pulverizing the pulverized mixture in a nitrogen gas atmosphere at a temperature of 1300 to 1500 ° C. Heat treatment for 2 to 5 hours; will be prepared by a method comprising;

The expanded graphite is prepared by mixing 100 parts by weight of sulfuric acid, 0.5 to 10 parts by weight of graphite, and 1 to 30 parts by weight of hydrazine at a temperature of 5 to 15° C. and depositing the graphite for 24 to 36 hours, washing and drying the deposited graphite to obtain graphite before expansion, and the expansion ratio ((volume of high expansion graphite)/(volume of graphite before expansion)) is 450 by expanding the graphite before expansion at a temperature of 500 to 800 ° C. for 10 to 30 minutes It may be one of high expansion graphite prepared by a method comprising the step of producing high expansion graphite to 600 times.

The polyrotaxane is a cyclodextrin cyclic molecule, a polybutadiene linear molecule that is skewered in the opening of the cyclodextrin cyclic molecule, and is disposed at both ends of the polybutadiene linear molecule to prevent detachment of the cyclodextrin cyclic molecule having a blocker that prevents;

All or part of the hydroxyl group of the cyclodextrin may be substituted with a sulfonic acid group or a sulfuric acid ester group.

The blocking group disposed at both ends of the polybutadiene linear molecule to prevent detachment of the cyclic cyclodextrin molecule may include an anthracene-sorbitol ethoxylate complex represented by the following formula (1).

[Formula 1]

In the above formula, n is an integer from 2 to 10.

In addition, another embodiment of the present invention is a road repair construction method using the polymer-modified super-velocity cement concrete composition having high strength and high durability,

removing deteriorated, damaged or contaminated parts of a concrete structure such as a road; cleaning the removed area; Primer or blooming treatment on the cleaned area; Restoring the cross section by pouring the polymer-modified super-velocity cement concrete composition having high strength and high durability on the primer or blooming-treated upper portion; applying a film curing agent to the upper portion of the polymer-modified super-fast cement concrete composition having high strength and high durability to inhibit plastic cracking by preventing moisture evaporation; And it provides a road repair construction method comprising the step of curing.

The polymer-modified super-velocity cement concrete composition having high strength and high durability according to an embodiment of the present invention and a road repair construction method using the same promotes initial hydration of cement and densification of the tissue, thereby enabling stable strength expression in the early stage. It has the effect of minimizing the traffic control period by enabling the early expression of high strength characteristics such as , compressive strength, flexural strength, and adhesive strength. In addition, the adhesion performance with the existing bridge pavement is excellent, and long-term high strength characteristics such as flexural strength and compressive strength are also very strengthened, thereby preventing surface cracking and expansion fracture of concrete. In addition, it has excellent resistance to freezing and thawing, neutralization and salt damage, and thus has the effect that the maintenance effect can be maintained for a long time with high durability.

Hereinafter, embodiments of the present invention will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

An embodiment of the present invention comprises 5 to 50% by weight of fine aggregate, 5 to 40% by weight of coarse aggregate, 0.1 to 10% by weight of water, 5 to 40% by weight of a super fast cement binder, and 1 to 30% by weight of a polymer modifier. A polymer-modified super-fast cement concrete composition having high strength and high durability;

The super fast cement binder is 100 parts by weight of crude Portland cement, 20 to 40 parts by weight of calcium sulfoaluminate, 1 to 20 parts by weight of heavy calcium carbonate, 1 to 20 parts by weight of electric furnace reduced slag, 1 to 20 parts by weight of titanium carbonitride , 1 to 20 parts by weight of alkali silicate, 0.1 to 10 parts by weight of graphite, and 0.1 to 10 parts by weight of magnesium fluoride;

The polymer modifier is styrene-methyl methacrylate-butadiene copolymer 100 parts by weight, ethylene-glycidyl methacrylate copolymer 70 to 90 parts by weight, acetoacetoxyethyl methacrylate 10 to 30 parts by weight, diacetone acrylic It provides a polymer-modified super-fast cement concrete composition having high strength and high durability, containing 10 to 30 parts by weight of amide, 0.1 to 10 parts by weight of polyrotaxane, and 0.1 to 10 parts by weight of polyglycerol-polyglycidyl ether.

The polymer-modified super-velocity cement concrete composition having high strength and high durability according to an embodiment of the present invention and a road repair construction method using the same promotes the initial hydration of cement and densification of the tissue, so that stable strength expression is possible at the beginning Of course, there is an effect that can minimize the traffic control period by enabling high-strength characteristics such as compressive strength, flexural strength, and adhesive strength to be expressed at an early stage. In addition, the adhesion performance with the existing bridge pavement is excellent, and long-term high strength properties such as flexural strength and compressive strength are also very strengthened, thereby preventing surface cracking and expansion fracture of concrete. In addition, it has excellent resistance to freezing and thawing, neutralization and salt damage, and thus has the effect that the maintenance effect can be maintained for a long time with high durability.

More specifically, the polymer-modified super-velocity cement concrete composition having high strength and high durability according to an embodiment of the present invention contains 5 to 50% by weight of fine aggregate, 5 to 40% by weight of coarse aggregate, 0.1 to 10% by weight of water, and 5 to 40% by weight of a cement binder, and 1 to 30% by weight of a polymer modifier.

The aggregate used in the present invention is divided into fine aggregate and coarse aggregate. Those having a particle diameter of 5 mm or less are called fine aggregates, and those having a particle diameter greater than 5 mm are classified as coarse aggregates. The fine aggregate is preferably contained in an amount of 5 to 50% by weight based on the polymer-modified super-velocity cement concrete composition having high strength and high durability of the present invention, and the coarse aggregate is polymer-modified super-velocity cement concrete having high strength and high durability according to the present invention It is preferably contained in an amount of 5 to 40% by weight based on the composition.

The super-velocity cement binder used in the present invention promotes the initial hydration of cement and densification of the tissue to make tight concrete, and it is possible to secure the initial strength after pouring, thereby greatly improving the curing speed of the mortar and minimizing the traffic control time. There is an effect that can be done. In addition, by mixing with the polymer modifier of the present invention, salt damage and freeze-thaw resistance can be greatly improved, and durability is strengthened, thereby ensuring long-term usability of the repaired road. In addition, there is an excellent effect of chemical resistance, water resistance and neutralization resistance. In addition, it has excellent adhesion performance with the existing bridge pavement, and mechanical properties such as flexural strength, tensile strength and compressive strength are very strengthened, thereby preventing surface cracking and expansion fracture of concrete.

In consideration of the above-described improvement effect, the cement binder is preferably contained in an amount of 5 to 40% by weight in the polymer-modified cementitious cement binder composition having high strength and high durability according to an embodiment of the present invention.

The super-velocity cement binder is 100 parts by weight of crude Portland cement, 20 to 40 parts by weight of calcium sulfoaluminate, 1 to 20 parts by weight of heavy calcium carbonate, 1 to 20 parts by weight of electric furnace reduced slag, and 1 to 20 parts by weight of titanium carbonitride. parts, 1 to 20 parts by weight of alkali silicate, 0.1 to 10 parts by weight of graphite, and 0.1 to 10 parts by weight of magnesium fluoride can be preferably used.

It is preferable to use the crude Portland cement specified in KS, and it is preferable to use a fineness of 5,000 to 9,000 cm2/g.

Hereinafter, the content of the components constituting the super-fast cement binder is based on 100 parts by weight of the crude Portland cement.

The calcium sulfoaluminate provides fast curing properties, and functions to exhibit super-fast curing properties.

The calcium sulfoaluminate is preferably contained in an amount of 20 to 40 parts by weight based on 100 parts by weight of the crude Portland cement. When the content of the calcium sulfoaluminate is too small, there is a problem that the above-described improvement effect may be insufficient. There is a problem in that price competitiveness may be lowered.

The heavy calcium carbonate makes the hydration structure of concrete dense, and functions to improve long-term strength, particulate filling effect, and durability such as impact resistance and fire resistance. In general, calcium carbonate is divided into two types: ground calcium carbonate produced by a physical processing method and light calcium carbonate produced by a chemical recrystallization method according to a manufacturing method. Calcium carbonate is produced by pulverizing and classifying white crystalline calcite, and preferably has a fineness of 5,500 to 9,500 cm2/g and an average particle diameter of 5 μm or less.

The ground calcium carbonate is preferably contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the crude steel portland cement. If the content of the ground calcium carbonate is too small, there is a problem that the above-described improvement effect may be insufficient, and if the content of the ground calcium carbonate is too large, fluidity deterioration and workability may be deteriorated due to the increase in the fineness of the ground calcium carbonate There is a problem.

The electric furnace reduction slag serves to promote a hydration reaction to exhibit crude rigidity, rapid hardening, and quick setting.

In general, in an electric furnace, oxidized slag is generated in the process of melting iron scrap with electric arc heat, blowing oxygen, and adding quicklime to remove impurities in the iron scrap, and the molten steel is re-processed with ferroalloy and quicklime in the secondary refining furnace. Reduced slag is generated in the process of removing _{O 2} and S by adding . Electric furnace reduction slag, which is an industrial by-product, contains a large amount of _{CaO, Al 2} O ₃ , Fe ₂ O ₃ , SiO _{2 ,} etc., although there may be slight differences between processes such as hot rolling, section steel, and steel bar processes.

More specifically, the electric furnace reduction slag is CaO 43 to 57 wt%, Al ₂ O ₃ 27 to 36 wt%, MgO 5.7 to 12.8 wt%, SO ₃ 0.8 to 3.4 wt%, Fe ₂ O ₃ 0.3 to 5 wt% and SiO ₂ 3.1 to 6.5 wt% may be used to further improve the above effect.

The electric furnace reduced slag is preferably contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the crude steel portland cement. When the content of the electric furnace reduction slag is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the electric furnace reduction slag is too large, the hardening rate is excessively fast and workability may be reduced. There is this.

The titanium carbonitride functions to improve durability, such as excellent strength, abrasion resistance, corrosion resistance, acid and salt resistance. In particular, by improving the lubricity of the composition, it functions to further prevent cracking of concrete by making the structure of the hydrated mineral more dense.

The titanium carbonitride is a step of preparing a mixture of titanium oxide (TiO ₂ ) powder and expanded graphite, pulverizing the mixture, and pulverizing the pulverized mixture in a nitrogen gas atmosphere at a temperature of 1300 to 1500 ° C. Heat treatment for 2 to 5 hours; prepared by a method comprising, the composition is in _{the range of TiC 0.3} N _0.7 to TiC _0.7 N _0.3 , and the average particle diameter is 10 nm to 50 μm. can do.

At this time, the expanded graphite is mixed with 100 parts by weight of sulfuric acid, 0.5 to 10 parts by weight of graphite, and 1 to 30 parts by weight of hydrazine at a temperature of 5 to 15 ° C. and depositing the graphite for 24 to 36 hours, washing the deposited graphite And drying to obtain graphite before expansion, and expanding the graphite before expansion at a temperature of 500 to 800 ° C. for 10 to 30 minutes to expand the ratio ((volume of high expansion graphite) / (volume of graphite before expansion)) It may be a high-expansion graphite prepared by a method comprising the step of producing a high-expansion graphite that is 450 to 600 times. At this time, the drying of the deposited graphite may be performed at a temperature of 85 to 105 ℃ for 2 to 10 hours.

The titanium carbonitride is preferably contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the crude steel portland cement. When the content of the titanium carbonitride is too small, there is a problem that the improvement effect may be weak, and when the content of the titanium carbonitride is too large, the manufacturing cost increases and the price competitiveness may decrease.

The alkali silicate is used to develop initial strength and improve durability. More specifically, the alkali silicate may be at least one selected from the group consisting of potassium silicate, lithium silicate, and mixtures thereof.

The alkali silicate is preferably contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the crude steel portland cement. When the content of the alkali silicate is too small, there is a problem that the above-mentioned improvement effect may be insufficient, and when the content of the alkali silicate is too large, there is a problem that the curing speed is excessively fast and workability may be deteriorated.

The graphite functions to increase abrasion resistance, durability and tensile strength.

In particular, the graphite has an average diameter of 1 to 10 μm and uses plate-shaped graphite having a thickness of 10 to 60 nm, so that the horizontal area is maximized and the function of preventing moisture movement can be performed superiorly, so that the chloride penetration resistance And there is an effect that can improve the improved durability, such as freeze-thaw stability according to temperature change. In addition, since the tensile strength increases when combined with other constituent materials of the latex-modified fast-hardening concrete composition having improved durability, including the graphite of the present invention, there is an effect of improving strength characteristics and workability.

The graphite is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the crude Portland cement. When the content of the graphite is too small, there is a problem that the above-mentioned improvement effect may be insufficient, and when the content of the graphite is too large, there is a problem that the initial strength expression may be delayed.

The magnesium fluoride functions to provide very improved durability such as salt penetration resistance and freeze-thaw resistance by improving abrasion resistance, corrosion resistance, chemical resistance and chemical resistance.

The magnesium fluoride has the effect of further improving the above-described improvement effect by using the one having the form of hollow magnesium fluoride particles.

More specifically, the hollow magnesium fluoride particles may be prepared by dissolving one or more magnesium precursors selected from the group consisting of magnesium acetate, magnesium citrate, magnesium sulfate, and hydrates thereof in a solvent to form a magnesium precursor solution; At least one fluorine precursor selected from the group consisting of sodium fluoride, potassium fluoride, ammonium fluoride, quaternary ammonium fluoride, and mixtures thereof, and ammonium hydroxide, ammonium chloride, ammonium sulfate, tetraethylammonium hydroxide, tetra dissolving at least one ammonium-based additive selected from the group consisting of ethylammonium bromide and a mixture thereof in a solvent to form a fluorine precursor solution; reacting the magnesium precursor solution with the fluorine precursor solution to precipitate magnesium fluoride; and after filtering and centrifuging the precipitated magnesium fluoride, heat treatment at a temperature of 300 to 500 °C for 1 to 5 hours at a temperature increase rate of 0.2 to 2 °C/min. The above effect can be further improved by using a thickness of 5 to 80 nm and a thickness of the magnesium fluoride film of 0.5 to 3 nm.

In this case, the solvent may preferably be one or more selected from the group consisting of water, methanol, ethanol, isopropanol, and mixtures thereof. In addition, in the reaction of the magnesium precursor solution and the fluorine precursor solution, the magnesium precursor solution and the fluorine precursor solution have a molar ratio of magnesium (Mg) and fluorine (F) included in each of 1:1 to 2 by mixing, the reaction may be carried out at a temperature of room temperature to 45 °C for 1 to 5 hours.

The magnesium fluoride is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the crude Portland cement. When the content of the magnesium fluoride is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the magnesium fluoride is too large, there is a problem that price competitiveness may be lowered.

On the other hand, the polymer modifier used in the present invention is styrene-methyl methacrylate-butadiene copolymer 100 parts by weight, ethylene-glycidyl methacrylate copolymer 70 to 90 parts by weight, acetoacetoxyethyl methacrylate 10 to 30 parts by weight, 10 to 30 parts by weight of diacetone acrylamide, 0.1 to 10 parts by weight of polyrotaxane, and 0.1 to 10 parts by weight of polyglycerol-polyglycidyl ether; It has excellent material and construction stability against external temperature changes, can provide excellent strength, highly improved durability such as salt penetration resistance, freeze-thaw resistance, etc., and has the effect of providing very improved workability.

In consideration of the above-described improvement effect, the polymer modifier is preferably included in an amount of 1 to 30% by weight of the polymer-modified super-fast cement concrete composition having high strength and high durability according to an embodiment of the present invention.

The styrene-methyl methacrylate-butadiene copolymer functions to improve excellent strength, bonding strength, and durability.

Hereinafter, the content of the components constituting the polymer modifier is based on 100 parts by weight of the styrene-methylmethacrylate-butadiene copolymer.

The ethylene-glycidyl methacrylate copolymer functions to improve excellent strength, bonding strength, water tightness and durability.

The ethylene-glycidyl methacrylate copolymer is preferably contained in an amount of 70 to 90 parts by weight based on 100 parts by weight of the styrene-methyl methacrylate-butadiene copolymer. When the content of the ethylene-glycidyl methacrylate copolymer is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the ethylene-glycidyl methacrylate copolymer is too large, curing is performed. There is a problem that may delay or lower price competitiveness.

The acetoacetoxyethyl methacrylate functions to implement high durability by improving elongation, flexural strength, chemical resistance and weather resistance.

The acetoacetoxyethyl methacrylate is preferably contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the styrene-methyl methacrylate-butadiene copolymer. When the content of the acetoacetoxyethyl methacrylate is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the acetoacetoxyethyl methacrylate is too large, curing is delayed or price competitiveness There is a problem that this can be degraded.

The diacetone acrylamide functions to realize high durability by improving excellent adhesion, bending-tensile strength, elasticity, chemical resistance and weather resistance.

The diacetone acrylamide is preferably contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the styrene-methyl methacrylate-butadiene copolymer. When the content of the diacetone acrylamide is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the diacetone acrylamide is too large, there is a problem that price competitiveness may be lowered.

The polyrotaxane improves workability by reducing bleeding of concrete, ensures uniform quality of concrete, improves watertightness and durability, and functions to very effectively inhibit shrinkage cracks.

The polyrotaxane is a cyclodextrin cyclic molecule, a polybutadiene linear molecule that is skewered in the opening of the cyclodextrin cyclic molecule, and is disposed at both ends of the polybutadiene linear molecule to dissociate the cyclodextrin cyclic molecule to have a blocker that prevents; By using that all or part of the hydroxyl groups of the cyclodextrin are substituted with sulfonic acid groups or sulfuric ester groups, the above-described effects can be further improved, and initial strength can be secured through rapid curing.

In this case, the blocking groups disposed at both ends of the polybutadiene linear molecule to prevent the detachment of the cyclodextrin cyclic molecule are dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes. Or it may be an anthracene.

More specifically, the blocking group disposed at both ends of the polybutadiene linear molecule to prevent detachment of the cyclodextrin cyclic molecule includes an anthracene-sorbitol ethoxylate complex represented by the following Chemical Formula 1 to achieve the above effect can be further improved.

[Formula 1]

In the above formula, n is an integer from 2 to 10.

The polyrotaxane is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the styrene-methylmethacrylate-butadiene copolymer. When the content of the polyrotaxane is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the polyrotaxane is too large, there is a problem that price competitiveness may be lowered.

The polyglycerol-polyglycidyl ether provides excellent miscibility with the super-fast cement binder and stably forms a watertight coating film, thereby improving excellent strength, resistance to freeze-thaw and salt damage, and durability. .

The polyglycerol-polyglycidyl ether is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the styrene-methyl methacrylate-butadiene copolymer. When the content of the polyglycerol-polyglycidyl ether is too small, there is a problem that the above-described improvement effect may be insufficient, and when the content of the polyglycerol-polyglycidyl ether is too large, curing is reduced or, There is a problem in that price competitiveness may be lowered.

The polymer-modified super fast cement concrete composition having high strength and high durability according to a preferred embodiment of the present invention comprises 5 to 50 wt% of fine aggregate, 5 to 40 wt% of coarse aggregate, and 5 to 40 wt% of super fast cement binder in a forced mixer. After stirring, 0.1 to 10% by weight of water and 1 to 30% by weight of a polymer modifier may be further mixed and stirred for a predetermined time (eg, 1 to 10 minutes).

In addition, another embodiment of the present invention is a road repair construction method using the polymer-modified super-velocity cement concrete composition having high strength and high durability,

removing deteriorated, damaged or contaminated parts of a concrete structure such as a road; cleaning the removed area; Primer or blooming treatment on the cleaned area; Restoring the cross section by pouring the polymer-modified super-velocity cement concrete composition having high strength and high durability on the primer or blooming-treated upper portion; applying a film curing agent to the upper portion of the polymer-modified super-fast cement concrete composition having high strength and high durability to inhibit plastic cracking by preventing moisture evaporation; And it provides a road repair construction method comprising the step of curing.

In this case, the deterioration part may be removed to the lower part where the reinforcing bar exists, and after cleaning the removed portion, removing the rust of the exposed reinforcing bar before the primer or blooming process may be further included.

In the case of chipping using a chipping device such as a crusher or a water jet in the step of removing the deteriorated part, the reinforcing bars of the concrete structure are not exposed in normal cases. In the case of exposure, a separate anti-rust treatment must be performed, but according to the present invention, a separate reinforcing bar anti-rust treatment is not required.

In the curing step, depending on the atmospheric conditions including the temperature, humidity, and wind strength of the site, 1) only the curing agent is sprayed, or 2) after the curing agent is sprayed, a vinyl or curing cloth is covered on the upper part and sprayed to a wet state or 3) after spraying the curing agent, it is recommended to apply the curing step separately while maintaining the warmth using vinyl, curing cloth, or a thermal insulation cover.

In particular, in the curing step, in the case of on-site atmospheric conditions (for example, in the case of atmospheric conditions with high atmospheric temperature (25 ℃ or more), low relative humidity, and windy conditions, such as in summer, vinyl, curing cloth, etc. Conversely, if the atmospheric temperature (below 25℃) is not high, relative humidity is high, and there is little wind, spray only curing agent and cure according to). After spraying, cover the top with vinyl, curing cloth, etc. In addition, when the atmospheric temperature is 5 ℃ or less, after spraying the curing agent, it may further include the step of performing thermal insulation curing using vinyl, curing cloth, insulation cover, etc.

Hereinafter, the primer or blooming treatment is used to refer to an operation of facilitating adhesion of the polymer-modified super-velocity cement concrete composition having high strength and high durability according to an embodiment of the present invention to a concrete structure.

As the primer material, at least one selected from SBR (Styrene Butadiene Rubber) latex, Poly Acryl Ester (PAE), epoxy emulsion, Ethyl Vinyl Acetate (EVA), and acrylic emulsion is selected. can be used

In addition, the blooming material is generally used in the art and the type thereof is not particularly limited, but a polymer modifier of the polymer-modified super-fast cement concrete composition having the high strength and high durability in the blooming material generally used in the art. can be mixed and used.

The polymer-modified super-velocity cement concrete composition having high strength and high durability according to an embodiment of the present invention and a road repair construction method using the same promotes initial hydration of cement and densification of the tissue, thereby enabling stable strength expression in the early stage. It has the effect of minimizing the traffic control period by enabling the early expression of high strength characteristics such as , compressive strength, flexural strength, and adhesive strength. In addition, the adhesion performance with the existing bridge pavement is excellent, and long-term high strength properties such as flexural strength and compressive strength are also very strengthened, thereby preventing surface cracking and expansion fracture of concrete. In addition, it has excellent resistance to freezing and thawing, neutralization and salt damage, and thus has the effect that the maintenance effect can be maintained for a long time with high durability.

As mentioned above, although preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the scope of the technical spirit of the present invention. This is possible.

<Production Example 1>

Production of titanium carbonitride

Preparing a mixture by mixing titanium oxide (TiO ₂ ) powder and carbon black so that a molar ratio of Ti: C is 1: 1, pulverizing the mixture, and placing the pulverized mixture in a nitrogen gas atmosphere was prepared by a method including; heat treatment at a temperature of 1400 ° C. for 5 hours, to prepare titanium carbonitride having an average particle diameter of 19 μm.

<Preparation Example 2>

Production of titanium carbonitride

Preparing a mixture by mixing titanium oxide (TiO ₂ ) powder and expanded graphite so that a molar ratio of Ti: C is 1: 0.7, pulverizing the mixture, and pulverizing the pulverized mixture in a nitrogen gas atmosphere at 1400 It was prepared by a method comprising a; heat treatment at a temperature of ℃ for 3 hours to prepare titanium carbonitride having an average particle diameter of 12 μm.

At this time, the expanded graphite is prepared by mixing 100 parts by weight of sulfuric acid and 2.5 parts by weight of graphite at a temperature of 5 ° C. and depositing graphite for 24 hours, washing the deposited graphite several times to remove sulfuric acid, and 7 at a temperature of 90 ° C. Drying for time to obtain graphite before expansion, and expanding the graphite before expansion at a temperature of 550 ° C. for 27 minutes so that the expansion ratio ((volume of high expansion graphite) / (volume of graphite before expansion)) is 187 times A high-expansion graphite prepared by a method including a step of preparing high-expansion graphite was used.

<Production Example 3>

Production of titanium carbonitride

Preparing a mixture by mixing titanium oxide (TiO ₂ ) powder and expanded graphite so that a molar ratio of Ti: C is 1: 0.7, pulverizing the mixture, and pulverizing the pulverized mixture in a nitrogen gas atmosphere at 1400 It was prepared by a method comprising a; heat treatment at a temperature of ℃ for 3 hours to prepare titanium carbonitride having an average particle diameter of 12 μm.

At this time, the expanded graphite is mixed with 100 parts by weight of sulfuric acid, 2.5 parts by weight of graphite, and 7.5 parts by weight of hydrazine at a temperature of 5 ° C. and depositing graphite for 24 hours, washing the deposited graphite several times to remove sulfuric acid, 90 Drying at a temperature of ℃ for 7 hours to obtain graphite before expansion, and expanding the graphite before expansion for 20 minutes at a temperature of 700 ℃ to the expansion ratio ((volume of high expansion graphite) / (volume of graphite before expansion) )) of high expansion graphite prepared by a method including the step of preparing 507 times high expansion graphite was used.

<Production Example 4>

Production of Magnesium Fluoride

As the magnesium fluoride, hollow magnesium fluoride particles were used.

In this case, the hollow magnesium fluoride particles are formed by dissolving magnesium acetate in water to form a magnesium precursor solution; Dissolving a fluorine precursor (ammonium fluoride) and an ammonium-based additive (ammonium chloride) in isopropanol to form a fluorine precursor solution; precipitating magnesium fluoride by mixing the magnesium precursor solution and the fluorine precursor solution in an amount such that a molar ratio of magnesium (Mg) and fluorine (F) is 1:2, and reacting at room temperature for 2 hours; and filtering and centrifuging the precipitated magnesium fluoride, followed by heat treatment at a temperature of 400 °C for 3 hours at a temperature increase rate of 1.5 °C/min, an average diameter of 55 nm, magnesium fluoride A film having a thickness of 2.5 nm was used.

<Preparation Example 5>

Preparation of polyrotaxane

As a polyrotaxane, a cyclodextrin cyclic molecule, a polybutadiene linear molecule that is skewered in the opening of the cyclodextrin cyclic molecule, and a polybutadiene linear molecule disposed at both ends of the cyclodextrin cyclic molecule to prevent detachment of the cyclodextrin cyclic molecule having a blocking group (anthracene group) that prevents; Among the hydroxyl groups of the cyclodextrin, those in which 50% were substituted with sulfate ester groups were used.

<Preparation Example 6>

Preparation of polyrotaxane

As a polyrotaxane, a cyclodextrin cyclic molecule, a polybutadiene linear molecule that is skewered in the opening of the cyclodextrin cyclic molecule, and a polybutadiene linear molecule disposed at both ends of the cyclodextrin cyclic molecule to prevent detachment of the cyclodextrin cyclic molecule having a blocker that prevents; Among the hydroxyl groups of the cyclodextrin, those in which 50% were substituted with sulfate ester groups were used.

In this case, the blocking group disposed at both ends of the polybutadiene linear molecule to prevent the detachment of the cyclic cyclodextrin molecule contains an anthracene group and an anthracene-sorbitol ethoxylate complex represented by Formula 1-1 in a molar ratio of 5 to 1 What was included was used.

[Formula 1-1]

In the above formula, n is 2.

<Examples and Comparative Examples>

The super-velocity cement binder, fine aggregate, and coarse aggregate mixed in the components and contents as shown in Table 1 below were put in a forced mixing mixer, and then mixed under dry mixing conditions for 3 minutes, and the components as shown in Table 1 and A polymer-modified super-fast cement concrete composition having high strength and high durability and a comparative concrete composition were prepared by mixing water and a polymer modifier at the same time and mixing for 1 minute and 30 seconds.

Category (wt%) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 fine aggregate 39 38 40 40 40 coarse aggregate 35 31 31 31 31 water 2 One One One One Super-velocity cement binder 19 23 21 21 21 (parts by weight) crude steel portland cement
(Powder: 6,210 ㎠/g) 100 100 100 100 100 Calcium sulfoaluminate 35 24 22 15 38 heavy calcium carbonate
(Powder: 5,830 ㎠/g) 17 11 5 25 - Furnace reducing slag ¹⁾ 10 15 17 15 - titanium carbonitride 7
(Production Example 1) 3
(Production Example 2) 3
(Production Example 3) - - lithium silicate 5 5 5 - - Graphite ²⁾ 2 2 2 - - magnesium fluoride One
(usual
magnesium fluoride powder) One
(usual
magnesium fluoride powder) One
(Production Example 4) - - ¹⁾ Electric furnace reduction slag: CaO 44.2% by weight, Al ₂ O ₃ 33.9% by weight, MgO 10.5% by weight, SO ₃ 1.08% by weight, Fe ₂ O ₃ 2.23% by weight and SiO ₂ 4.74% by weight is used
²⁾ Use plate-shaped graphite with average diameter: 3.5 μm and thickness: 23 nm polymer modifier 5 7 7 7 7 (parts by weight) Styrene-methylmethacrylate-butadiene copolymer 100 100 100 100 100 Ethylene-glycidyl methacrylate copolymer 75 80 82 78 - Acetoacetoxyethyl methacrylate 16 14 16 - - diacetone acrylamide 12 10 10 - - polyrotaxane 4
(Production Example 5) 5
(Production Example 5) 5
(Production Example 6) - - Polyglycerol-polyglycidyl ether 5 3 3 - -

The following test examples are experiments comparing the characteristics of Examples 1 and 2 according to the present invention with those of Comparative Examples 1 and 2 in order to more easily understand the characteristics of Examples 1 to 3 according to the present invention disclosed above. the results are shown.

<Test Example 1>

According to the method specified in KS F 2402, the polymer-modified super-velocity cement concrete composition having high strength and high durability of Examples 1 to 3 described above and the comparative concrete compositions prepared according to Comparative Examples 1 and 2 were prepared. It shows the results of the slump test (the degree of dough). The slump test tests the toughness of the dough, such as the softness and consistency of concrete, and the higher the number, the better the workability, that is, the workability when pouring concrete.

Table 2 below shows the change in slump over time.

division Slump (cm) Immediately after stirring after 20 minutes after 30 minutes after 40 minutes after 60 minutes Example 1 18 18 16 15 13 Example 2 18 17 16 14 13 Example 3 19 18 17 15 14 Comparative Example 1 9 7 5 2 One Comparative Example 2 11 9 6 4 2

As shown in Table 2, it was confirmed that Examples 1 to 3 according to the present invention had excellent workability compared to Comparative Examples 1 and 2.

<Test Example 2>

Compressive strength of the polymer-modified super-velocity cement concrete composition having high strength and high durability according to Examples 1 to 3 and the comparative concrete compositions prepared in Comparative Examples 1 and 2 according to the method specified in KS F 2405 The test results are shown.

Table 3 below shows the change in compressive strength over time.

division Compressive strength (kgf/㎠) after 3 hours after 12 hours after 24 hours 3 days later 28 days later Example 1 318 347 362 407 499 Example 2 325 358 370 427 512 Example 3 337 365 376 435 529 Comparative Example 1 - - - 195 357 Comparative Example 2 - - - 165 325

As shown in Table 3, in Examples 1 to 3 according to the present invention, it is possible to perform another operation on the poured concrete because it is easy to harden quickly. It can be seen that the implementation is difficult. In addition, it was confirmed that Examples 1 to 3 were superior to Comparative Examples 1 and 2 according to the present invention in compressive strength after complete curing.

<Test Example 3>

The flexural strength of the polymer-modified super-velocity cement concrete composition having high strength and high durability of Examples 1 to 3 and the comparative concrete compositions prepared in Comparative Examples 1 and 2 according to the method specified in KS F 2408 was measured. one result is shown.

Table 4 below shows the change in flexural strength over time.

division Warp (kgf/㎠) after 3 hours after 12 hours after 24 hours 3 days later 28 days later Example 1 74 88 91 108 126 Example 2 79 91 95 110 134 Example 3 81 95 97 113 137 Comparative Example 1 - - - 61 78 Comparative Example 2 - - - 38 49

As shown in Table 4, in Examples 1 to 3 according to the present invention, rapid hardening proceeded and no deformation of concrete occurred, but Comparative Examples 1 and 2 had a slow curing progress, so when an external load was applied It can be confirmed that the poured concrete can be damaged or deformed. In addition, it was confirmed that Examples 1 to 3 were superior to Comparative Examples 1 and 2 in flexural strength after complete curing.

<Test Example 4>

Adhesive strength of the polymer-modified super-velocity cement concrete composition having high strength and high durability of Examples 1 to 3 and the comparative concrete compositions prepared in Comparative Examples 1 and 2 according to the method specified in KS F 2762 was measured. was measured, and the results are shown in Table 5.

division Adhesive strength (kgf/㎠) after 3 hours after 12 hours after 24 hours 3 days later 28 days later Example 1 21 24 25 27 29 Example 2 23 26 27 30 31 Example 3 25 27 28 31 32 Comparative Example 1 - - - 16 19 Comparative Example 2 - - - - 11

As shown in Table 5, it was confirmed that Examples 1 to 3 according to the present invention had superior adhesive strength compared to Comparative Examples 1 and 2.

<Test Example 5>

The method specified in KS F 4004 (cement bricks) for the polymer-modified super-velocity cement concrete composition having high strength and high durability of Examples 1 to 3 and the comparative concrete compositions prepared according to Comparative Examples 1 and 2 The absorption rate was measured according to the method, and the results are shown in Table 6. If the water absorption rate is high, if impurities or water penetrate into the interior of the concrete, the porosity increases in the interior of the concrete, causing a problem that causes damage to the structure. That is, the lower the water absorption, the higher the strength of the concrete after hardening.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Absorption rate (%) 1.3 1.0 0.8 5.5 9.2

As shown in Table 6, it was confirmed that Examples 1 to 3 according to the present invention had a lower water absorption than Comparative Examples 1 and 2.

<Test Example 6>

The polymer-modified super-velocity cement concrete composition having high strength and high durability of Examples 1 to 3 and the comparative concrete compositions prepared in Comparative Examples 1 and 2 were freeze-thawed according to the method specified in KS F 2456. A resistance test was performed, and the durability index results of each of Examples and Comparative Examples according to the freeze-thaw resistance test are shown in Table 7. Freeze-thaw refers to the freezing and melting of moisture absorbed in concrete. If freeze-thaw is repeated, microcracks occur in the concrete structure, which leads to a problem of reduced durability.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 durability index 93 95 97 78 42

As shown in Table 7, it was confirmed that Examples 1 to 3 according to the present invention were superior in durability, ie, freeze-thaw resistance, compared to Comparative Examples 1 and 2.

<Test Example 7>

The polymer-modified super-velocity cement concrete composition having high strength and high durability of Examples 1 to 3 and the comparative concrete compositions prepared according to Comparative Examples 1 and 2 were subjected to KS F 2424 (Test method for changing the length of concrete) was measured for drying shrinkage, and the results are shown in Table 8 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Drying shrinkage (×10 ^-4 ) 1.0 1.0 0.8 2.7 2.1

As shown in Table 8, in Examples 1 to 3 according to the present invention, it was confirmed that the drying shrinkage amount was reduced compared to Comparative Examples 1 and 2.

<Test Example 8>

The polymer-modified super-velocity cement concrete composition having high strength and high durability of Examples 1 to 3 and the comparative concrete compositions prepared according to Comparative Examples 1 and 2 were prepared according to JIS A 1171 (Test method for polymer cement mortar). was performed, and the results are shown in Table 9.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Neutralization depth (mm) 0.7 0.3 0.2 2.1 3.5

As shown in Table 9, it was confirmed that Examples 1 to 3 according to the present invention showed less neutralization penetration than Comparative Examples 1 and 2.

<Test Example 9>

A test according to JIS A 1171 was performed on the polymer-modified super-velocity cement concrete composition having high strength and high durability of Examples 1 to 3 and the comparative concrete compositions prepared according to Comparative Examples 1 and 2, and the The results are shown in Table 10 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Chloride ion penetration depth (mm) 1.8 1.4 1.0 3.1 8.4

As shown in Table 10, in Examples 1 to 3 according to the present invention, it was confirmed that the chloride ion penetration depth was small compared to Comparative Examples 1 and 2.

As described above, those skilled in the art to which the present invention pertains will understand that the present invention may be implemented in other specific forms without changing the technical spirit or essential characteristics thereof. Therefore, it should be understood that all of the embodiments described above are illustrative and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention, rather than the above detailed description, all changes or modifications derived from the meaning and scope of the claims to be described later and their equivalents.

Claims (5)

A polymer having high strength and high durability, comprising 5 to 50% by weight of fine aggregate, 5 to 40% by weight of coarse aggregate, 0.1 to 10% by weight of water, 5 to 40% by weight of a super fast cement binder, and 1 to 30% by weight of a polymer modifier A modified priming cement concrete composition;
The super fast cement binder is 100 parts by weight of crude Portland cement, 20 to 40 parts by weight of calcium sulfoaluminate, 1 to 20 parts by weight of heavy calcium carbonate, 1 to 20 parts by weight of electric furnace reduced slag, 1 to 20 parts by weight of titanium carbonitride , 1 to 20 parts by weight of alkali silicate, 0.1 to 10 parts by weight of graphite, and 0.1 to 10 parts by weight of magnesium fluoride;
The polymer modifier is styrene-methyl methacrylate-butadiene copolymer 100 parts by weight, ethylene-glycidyl methacrylate copolymer 70 to 90 parts by weight, acetoacetoxyethyl methacrylate 10 to 30 parts by weight, diacetone acrylic 10 to 30 parts by weight of amide, 0.1 to 10 parts by weight of polyrotaxane, and 0.1 to 10 parts by weight of polyglycerol-polyglycidyl ether;
The polyrotaxane is a cyclodextrin cyclic molecule, a polybutadiene linear molecule that is skewered in the opening of the cyclodextrin cyclic molecule, and is disposed at both ends of the polybutadiene linear molecule to prevent detachment of the cyclodextrin cyclic molecule having a blocker that prevents;
A polymer-modified super-fast cement concrete composition having high strength and durability, characterized in that all or part of the hydroxyl groups of the cyclodextrin are substituted with sulfonic acid groups or sulfuric ester groups.
According to claim 1,
The titanium carbonitride is
Preparing a mixture of titanium oxide (TiO ₂ ) powder and expanded graphite, pulverizing the mixture, and pulverizing the pulverized mixture at a temperature of 1300 to 1500° C. in a nitrogen gas atmosphere for 2 to 5 hours It is prepared by a method comprising; heat-treating;
The expanded graphite is
A step of depositing graphite for 24 to 36 hours by mixing 100 parts by weight of sulfuric acid, 0.5 to 10 parts by weight of graphite, and 1 to 30 parts by weight of hydrazine at a temperature of 5 to 15 ° C. Washing and drying the deposited graphite to obtain graphite before expansion The expansion ratio ((volume of high expansion graphite)/(volume of graphite before expansion)) is 450 to 600 times by expanding the graphite before expansion at a temperature of 500 to 800 ° C for 10 to 30 minutes to obtain a A polymer-modified super-fast cement concrete composition having high strength and high durability, characterized in that it is high expansion graphite prepared by a method comprising the step of preparing expanded graphite.
delete According to claim 1,
Blocking groups disposed at both ends of the polybutadiene linear molecule to prevent detachment of the cyclic cyclodextrin molecule
A polymer-modified super-fast cement concrete composition having high strength and high durability, characterized in that it comprises an anthracene-sorbitol ethoxylate complex represented by the following formula (1).
[Formula 1]

In the above formula, n is an integer from 2 to 10.
A method for repairing and constructing a road using the polymer-modified super-velocity cement concrete composition having high strength and high durability according to any one of claims 1, 2 and 4,
removing deteriorated, damaged or contaminated parts of a concrete structure such as a road; cleaning the removed area; Primer or blooming treatment on the cleaned area; Restoring the cross section by pouring the polymer-modified super-velocity cement concrete composition having high strength and high durability on the primer or blooming-treated upper portion; applying a film curing agent to the upper portion of the polymer-modified super-fast cement concrete composition having high strength and high durability to inhibit plastic cracking by preventing moisture evaporation; And Road repair construction method comprising the step of curing.