KR100516258B1 - Filling composite for crack repairability of concrete structures and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a crack filling repair material composition and a method for manufacturing the same, the object of which is to provide a composite function capable of simultaneously exhibiting the properties of the reactive organic material and the advantages of the inorganic material, excellent adhesion, water resistance, water repellency The present invention provides a crack filling repair material composition having a durability, elasticity, void filling property, and capable of exhibiting self-cleaning performance to prevent mold and moss generation, and a method of manufacturing the same.

The present invention provides a crack filling repair composition; The crack filling repair material is 10 to 47% by weight of thermosetting resin, 5 to 20% by weight of low molecular weight polypropylene glycol having a molecular weight of about 400, 1 to 3% by weight of curing catalyst for organotin compounds, and non-reactive organopolysiloxane represented by Chemical Formula 1 -10 to 20% of the polyoxyalkylene copolymer as an essential component, the remainder is provided with a crack filling repair material composition and a method for producing the same filled with inorganic powders such as cement, calcium carbonate, talc, clay, fine powder silica, diatomaceous earth, etc. have.

Formula 1

In this formula, R is arbitrary group chosen from mutually independent hydrogen group or monovalent hydrocarbon group, m is 0-10, n is 1-10, ｘ is 2-6, y is 3-10, ｚ is 0 -10 is shown, and A is a monovalent hydrocarbon group.

Description

Filling composite for crack repairability of concrete structures and method for manufacturing the same

The present invention relates to a crack filling repair material composition and a method for manufacturing the same. The present invention relates to the filling of cracks occurring in building materials such as mortar, concrete, and stone, and the like, and thus, adhesiveness, water resistance, water repellency, mold resistance, self-cleaning property, and low friction property. And a crack filling repair material composition capable of imparting crack followability and the like and a method of manufacturing the same.

In general, various reactive organic materials or inorganic materials are used for the purpose of imparting adhesiveness, waterproofness, water repellency, low friction, release property, etc. to cracks generated in construction structures such as mortar, concrete, and stone. In particular, urethanes and epoxies are widely used as crack filling repair materials because they have good workability as a liquid, can change the performance of the cured coating film, can be colored, and are also advantageous in terms of cost.

However, the penetration and adhesion of building materials such as mortar, concrete, and stone, etc., may not be sufficient. For example, in the case of repairing cracks, fine microcracks and voids around cracks to be repaired As it does not penetrate into the deep part of the crack inside the substrate, problems such as insufficient strength and insufficient durability occur. In particular, after hardening, interfacial dropping with the crack end due to volume shrinkage and repair traces Problems such as deterioration of the aesthetic appearance of boys also occur.

In addition, inorganic crack filling repair materials made by mixing water-dispersible emulsions such as acrylic, EVA, SBR, etc. with cement are simply filled with crack cracks, which are non-adhesive, and in case of completely dried cracks or wet cracks, There are various problems such as defects such as poor curing due to excessive absorption of water required for absorption or hydration reaction, or interface dropout due to curing shrinkage.

The present invention has been made in consideration of the above problems, and its object is to have a composite function capable of simultaneously exhibiting the properties of the reactive organic material and the advantages of the inorganic material, thereby providing excellent adhesion, water resistance, water repellency, and durability. In addition, the present invention provides a crack filling repair material composition having elasticity and void filling properties and capable of exhibiting self-cleaning performance to prevent the occurrence of mold and moss, and a method of manufacturing the same.

The present invention provides a crack filling repair composition; The crack filling repair material represented by 10 to 47% by weight of the thermosetting resin represented by the formula (2), 5 to 20% by weight of low molecular weight polypropylene glycol having a molecular weight of about 400, 1 to 3% by weight of the curing catalyst of the organic tin compound 10 to 20% of the non-reactive organopolysiloxane-polyoxyalkylene copolymer which is used as an essential component, and the remainder is crack-filled repair material composition filled with inorganic powders such as cement, calcium carbonate, talc, clay, fine powder silica, diatomaceous earth, and the like To provide a manufacturing method.

Formula 1

In this formula, R is arbitrary group chosen from mutually independent hydrogen group or monovalent hydrocarbon group, m is 0-10, n is 1-10, ｘ is 2-6, y is 3-10, ｚ is 0 -10 is shown, and A is a monovalent hydrocarbon group.

Formula 2

In the present invention, an inorganic powder is added to an appropriate amount of thermosetting resin, mixed with a stirrer, and a specific amount of a curing accelerator catalyst is added to a specific non-reactive organopolysiloxane-polyoxyalkylene copolymer. After the aging solution is left to mature, polypropylene glycol, which is a lubricant, and an inorganic powder are added to the aging solution, mixed with a stirrer to form a cured material, and the main material and the cured material are mixed in a weight ratio of 1: 1.

The specific non-reactive organopolysiloxane-polyoxyalkylene copolymer is an essential component of the present invention, and mainly serves to prevent the occurrence of mold or moss by imparting permeability to the substrate, diffusibility, or self-cleaning property to the resin. It is represented by following General formula (1).

Formula 1

In the formula, R is any group selected from mutually independent hydrogen group or monovalent hydrocarbon group, m is 0-10, n is 1-10, x is 2-6, y is 3-10, z is 0- 10 represents, and A represents a monovalent hydrocarbon group.

The thermosetting resin is a glass resin, melamine resin, polyamide resin, polyimide resin, polyester resin, alkyd resin, epoxy resin, franc resin, polyurethane isocyanate resin, silicone resin, phenol resin, resorcinool resin, such resin And a composite resin with other polymers or low molecular weight compounds, although not particularly limited, isocyanate resins which are curable resins of isocyanate compounds are particularly preferred.

The isocyanate compound in the present invention is a compound having an isocyanate group in the molecule, and is not particularly limited, but is preferably a nurate-type modified body represented by the following formula (2). In addition, although R 'does not specifically limit, A C2-C20 hydrocarbon group is preferable.

Formula 2

In addition, the present invention may use a curing accelerator catalyst in the curing reaction, wherein the curing accelerator catalyst used is tin octylate, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin macaput, dibutyl tin Organotin compounds such as thiocarboxylate, dibutyl tin dimaleate, dibutyl tin occite, monobutyl tin oxide, geocutyl tin diocarboxylate, diocutyl tin macachift, and organic zinc compounds such as zinc octenate Organic mercury compounds such as phenyl mercury propionate, organic antimony compounds, potassium, sodium, calcium, magnesium, mercury, nickel, cobalt, zinc carbonates such as zinc, aluminum, tin, vanadium, titanium, dibutylamine-2-ethylhexate Amic acid, other acidic catalysts, basic catalysts, and the like, of which, although not particularly limited, organotin compounds are preferred.

The inorganic powder is mixed with a waterproof resin composition composed of the thermosetting resin and the non-reactive organopolysiloxane-polyoxyalkylene copolymer so as to have weight and the same physical properties as those of construction structures such as cement, mortar, and stone. , Calcium carbonate, talc, clay, fine powder silica, diatomaceous earth and the like can be used, and the mixing amount of such inorganic powder is not particularly limited.

In addition, in order to improve such work problems, it may be added and mixed with a lubricant such as polypropylene glycol, etc., but the added lubricant such as polypropylene glycol may be finely cracked by using a small molecule having a molecular weight of about 400. It may have a viscosity that can be deeply charged.

In addition, the mixing amount of the lubricant is preferably about 0.1 to 1 times the weight of the isocyanate resin, and if it is 0.1 or less, the viscosity rises and the workability is decreased. Because.

Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1

In order to confirm the curability of the curable resin composition essential for the present invention, 0.2 g / cm ² was placed on a 10 cm × 10 cm glass plate for a test sample having a mixed amount of an isocyanate compound and a specific non-reactive organopolysiloxane-polyoxyalkylene copolymer. After the coating, the coating film was allowed to stand at room temperature for 24 hours, and the state of the coating film was evaluated. The results are shown in Table 1 below.

At this time, the detail of the symbol described as (circle): hardening and (triangle | delta): One hardening remains sticky, and x shows not hardening.

Table 1

As shown in Table 1 above, in a mixed amount, 0 to 100% of isocyanate resin compound, 0 to 3% of organic tin compound, and 0 to 97% of specific non-reactive organopolysiloxane-polyoxyalkylene copolymer are different. As a result of the mixing test, it was found that a mixture of 42 to 92% of isocyanate compounds and 5 to 55% of specific non-reactive organopolysiloxane-polyoxyalkylene copolymers with 3% of the organotin compound as a curing catalyst showed the best curing condition. Can be.

Example 2

Next, in order to confirm the curability after mixing inorganic powders such as cement, calcium carbonate, talc, clay, fine powder silica, diatomaceous earth, etc., which are essential for the present invention, the waterproof resin composition in the same manner as in Example 1 above. And inorganic powder, in this case, a typical calcium carbonate, as a representative example, a test sample having a different mixing amount was applied to a glass plate of 10 cm x 10 cm so as to be 2.0 g / cm 2, and placed at room temperature for 24 hours, and then the state of the coating film was evaluated. Is shown in Table 2, the details of the symbol notation as shown: ○: hardening, △: hardening, one sticky remains, ×: indicates not curing.

In the case of the crack-filling repairing material of the present invention, since adhesion, waterproofness, water repellency, strength, durability, and the like with the following base material to be repaired are required, tests for properties such as adhesion with the base material, waterproofness, water repellency, and strength are here. The adhesion was poured between two specimens of cement mortar having a size of 4 cm × 4 cm × 4 cm spaced at 0.1 cm intervals, left for 7 days, and then measured for adhesion in kgf / cm 2 using a universal testing machine.

Water repellency was applied to the cement mortar plate of 1cm, 10cm × 10cm in thickness and left to cure for 7 days. Then, water was dropped on it to confirm that water droplets formed. ○: Very good, △: Good, X: Slightly good.

In addition, the water resistance was evaluated for water permeability of the test body subjected to the water repellency test by using a mortar permeability tester at a test water pressure of 1 kg / cm ² , and the symbols indicated are ○: not permeable, △: not permeable but wet, ×: It is transmitted.

TABLE 2

Number One 2 3 4 5 6 7 8 9 10 11 Non-reactive Organic Polysiloxane-Polyoxyalkylene Copolymer (% by weight) 50 45 40 35 30 25 20 15 10 5 One Organotin Compounds (wt%) 3 3 3 3 3 3 3 3 3 3 3 Isocyanate Compound (wt%) 47 47 47 42 37 32 27 22 17 12 6 Calcium Carbonate (wt%) - 5 10 20 30 40 50 60 70 80 90 Evaluation results Curable ○ ○ ○ ○ ○ ○ ○ ○ △ △  × Adhesion 48 37 36 31 25 24 21 20 16 15 11 Water repellency ○ ○ ○ ○ ○ ○ ○ ○ ○ △  × Waterproof ○ ○ ○ ○ ○ ○ ○ ○ ○ △  ×

In a mixed amount as in Example 2, a mixed amount of 6 to 47% of isocyanate resin compound, 3% of organic tin compound, 1 to 50% of specific non-reactive organopolysiloxane-polyoxyalkylene copolymer and 5 to 90% of calcium carbonate was added. As a result of different tests, 3% of organic tin compound as a curing accelerator catalyst, 22 to 47% of isocyanate resin compound, 15 to 50% of specific non-reactive organopolysiloxane-polyoxyalkylene copolymer, and calcium silicate of inorganic powder It can be seen that the mixture of -60% shows the best state.

Example 3

Next, in order to confirm the filling property to the base material after mixing inorganic powders such as cement, calcium carbonate, talc, clay, fine powder silica, diatomaceous earth, etc., to the curable resin composition essential for the present invention, As a typical example, a test sample with a different amount of mixing was used as a representative example of a waterproof resin composition and an inorganic powder, and a general calcium carbonate was cut in half in the height direction of a columnar concrete having a diameter of 10 cm and a height of 40 cm. It was injected using an injection syringe for crack repair, and the injected depth was measured in cm.

On the other hand, the filling depth of the crack filling repair material closely relates to the viscosity and lubricity of the repair material. Therefore, here, polypropylene glycol having a molecular weight of 400 was added as a material for adjusting the viscosity and friction resistance of the crack filling repair material of the present invention, and the viscosity was measured in units of cPs using a rotational viscometer, and the curing state and depth of filling were measured. Was evaluated, and the results are shown in Table 3. At this time, the detail of the symbol to be shown represents (circle): good, (triangle | delta): slightly good, and x: bad.

TABLE 3

In the mixed amount as in Example 3, 2 to 47% of isocyanate resin compounds, 3% of organic tin compounds as curing accelerators, 10 to 20% of specific non-reactive organopolysiloxane-polyoxyalkylene copolymers, and 35 to 55 calcium carbonates As a result of the mixing test of varying the mixing amount with 5 to 20% of polypropylene glycol having a molecular weight of 400 and a molecular weight of 400, the viscosity decreases and the filling depth increases as the amount of polypropylene glycol added increases. However, the content of the isocyanate resin compound is not cured only when the content of the isocyanate resin compound is 2 to 7%, and when polypropylene glycol is added, the mixing amount of the isocyanate resin compound should be at least 10% or more of the total weight of the crack filler repair composition. I knew it was good.

Example 4

Next, the mold and self-cleaning properties of the crack filling repair material of the present invention was evaluated. For the mold resistance, a mortar plate of 50 mm x 50 mm x 25 mm was used for one year, and a part of the water storage unit of the outdoor cooling device of the water-cooled air conditioner was A submerged mold was used to immerse the mold. At this time, the mold was removed with a wire brush and then dried, and the sample was applied to 2.0 g / cm ² and cured at room temperature for 24 hours. Next, this test piece was partially submerged in the water storage part of the outdoor cooling apparatus of the water-cooled air conditioner in the same manner as described above to evaluate the state of the coating film after one year.

Comparative Example 1

At this time, the mold, which was not coated with the crack filling repair material of the present invention, was removed with a wire brush and dried to install a mortar as a test piece, and it was confirmed that the mold had propagated on the entire surface after one year.

The test results of Example 4 and Comparative Example 1 are shown in Table 4, the symbol denoted as in Example 4 and Comparative Example 1 ◎: No mold is generated on the coated surface, ○: 50% or less of the coated surface area Mold occurs in the area of △: Mold occurs in an area of 50% or more of the coated surface area, and ×: Mold occurs in the entire coated surface.

In addition, about self-cleaning, draw a line with an oil-based black pen on the cured coating film which completed the hardening test in Example 2, leave it at room temperature for 24 hours, wipe off with a damp cloth, and then wash the surface state of a coating film. Evaluated. At this time, the details of the symbol denoted as follows: ○: not contaminated at all, △: more than 50% of the contamination can be removed, but black traces are left, ×: indicates that some of the contamination can be removed.

Table 4

It can be seen from Table 4 that the crack filling repair material of the present invention is excellent in antifungal moldability and self-cleaning properties, in particular, non-reactive organopolysiloxane-polyoxyalkylene copolymer 27 to 50%, organotin compound as a curing accelerator catalyst The test result of mixing 5% to 50% of calcium carbonate to 3% to 27% to 47% of isocyanate resin compound showed excellent antifungal and self-cleaning properties.

The crack filling repair material of the present invention as described above can be arbitrarily selected as a one-liquid type, two-liquid type, or more according to the difference in packing form thereof, and the filling amount for the substrate is not particularly limited.

In addition, the present invention is not limited to the above-described specific preferred embodiments, and various modifications can be made by those skilled in the art without departing from the gist of the invention as claimed in the claims. Of course, such changes are within the scope of the claims.

As described above, the present invention contains thermosetting resins, in particular isocyanate resins, specific non-reactive organopolysiloxane-polyoxyalkylene copolymers, and inorganic powders, and thus has excellent permeability and diffusivity to the substrate. It penetrates deep into the micro parts and internal parts of cracks and repair parts such as building materials and stone, and after curing, it can exhibit elasticity, adhesiveness, and void filling property in addition to excellent waterproofness, strength, and durability.

In addition, the inorganic powder can make the physical properties of the cracked part after filling the same as a building material such as concrete or mortar, or stone, thereby giving a sense of unity. Also, the elasticity to be given is applied to the expansion and contraction of the cracked part due to the change in ambient temperature. Correspondingly, defects such as interface dropout can be prevented.

In addition, the crack filling repair material of the present invention to prevent the self-cleaning and the generation of mold or moss, and to prevent the aging or whitening phenomenon due to the waterproof effect, salt prevention effect, freeze damage effect, alkali aggregate reaction or neutralization In addition to the effects, it is excellent in heat resistance, cold resistance, weather resistance, and chemical resistance, so that there are many effects such as maintaining long-term durability and beautiful aesthetics of building materials such as concrete and mortar after crack filling and stone.

Claims (8)

In a crack fill repair composition; The crack filling repair material 10-47% of thermosetting resin, 5-20% of low molecular weight polypropylene glycol having a molecular weight of about 400, 1 to 3% curing accelerator catalyst, 10 to 20% of a non-reactive organopolysiloxane-polyoxyalkylene copolymer represented by Formula 1 below, The remainder is a crack filling repair composition, characterized in that consisting of inorganic powder. Formula 1 In this formula, R is arbitrary group chosen from mutually independent hydrogen group or monovalent hydrocarbon group, m is 0-10, n is 1-10, ｘ is 2-6, y is 3-10, ｚ is 0 -10 is shown, and A is a monovalent hydrocarbon group. The method of claim 1; A crack filling repair composition comprising a low molecular weight polypropylene glycol as a lubricant to the crack filling repair composition comprising the thermosetting resin and the non-reactive organopolysiloxane-polyoxyalkylene copolymer, an inorganic powder and a curing accelerator. The method of claim 1 or 2; The thermosetting resin is a glass resin, melamine resin, polyamide resin, polyimide resin, polyester resin, alkyd resin, epoxy resin, franc resin, polyurethane isocyanate resin, silicone resin, phenol resin, resorcinool resin, such resin And a composite resin of other polymers or low molecular weight compounds. The method of claim 1 or 2; The thermosetting resin is crack filling repair composition, characterized in that the isocyanate resin. The method of claim 4; The isocyanate resin is a crack filling repair composition, characterized in that the resin obtained from the Nurate-type modified resin represented by the formula (2) below. Formula 2 R 'is a C2-C20 hydrocarbon group at this time. The method of claim 1; The curing accelerator catalyst is tin octylate, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin macapatide, dibutyl tin thiocarboxylate, dibutyl tin dimaleate, dibutyl tin orcisite, monobutyl Organotin compounds such as tin oxide, geocutyl tin diocarboxylate, and diocutyl tin macachift; Organic zinc compounds such as zinc octenate; Organic mercury compounds such as phenyl mercury propionate; Organic antimony compounds, potassium, sodium, calcium, magnesium, mercury, nickel, cobalt, carboxylates such as zinc, aluminum, tin, vanadium, titanium, amine acids of dibutylamine-2-ethylhexate, other acidic catalysts, and Crack filling repair composition, characterized in that selected from the group consisting of a basic catalyst. The method of claim 1; The inorganic powder is crack filling repair composition, characterized in that selected from the group consisting of cement, calcium carbonate, talc, clay, fine powder silica, diatomaceous earth. In the crack filling repair material composition manufacturing method; The crack filling repair material, adding an inorganic powder to an appropriate amount of thermosetting resin and mixing with a stirrer as a main material; Adding an appropriate amount of a curing accelerator catalyst to the non-reactive organopolysiloxane-polyoxyalkylene copolymer represented by Formula 1 below, and aging by leaving at least 7 days at room temperature for 20 days; Adding a polypropylene glycol, which is a lubricant, and an inorganic powder to the aging solution after completion of aging to mix with a stirrer to form a hardening material; Method for producing a crack filling repair material composition comprising the step of mixing the main material and the hardener in a weight ratio of 1: 1. Formula 1 In this formula, R is arbitrary group chosen from mutually independent hydrogen group or monovalent hydrocarbon group, m is 0-10, n is 1-10, ｘ is 2-6, y is 3-10, ｚ is 0 -10 is shown, and A is a monovalent hydrocarbon group.