KR101804353B1 - A organic-inorganic hybrid composition for upper coating and a process of modifying the surface of a concrete or steel structure for enhancing anti-fouling property - Google Patents

Abstract

The present invention relates to a hybrid coating composition, a production method thereof, and a surface treatment method to protect steel materials or concrete using the same. More specifically, advantageous features of organic resins and inorganic resins can be exhibited by using a hybrid coating composition as a primer material containing an epoxy-silicone resin as a main ingredient while using an organic/inorganic hybrid top coating composition for top coat, and then coating surfaces of the steel material or concrete using the same. According to the present invention, it is possible to apply the same as hybrid coating compositions capable of preventing deterioration due to external factors and ensuring excellent adhesiveness, air permeability, and anti-fouling effects.

Description

Technical Field [0001] The present invention relates to an organic-inorganic hybrid coating composition and a surface treatment method for protecting concrete or steel using the same,

The present invention relates to an organic-inorganic hybrid top coat composition and a surface treatment method for protecting concrete or steel material for strengthening stain resistance using the same.

Concrete is a very common building material, but cracks are easy to occur, and through this cracks, the penetration of liquids and gases, which can corrode the concrete and the reinforcing bars in the concrete, is easy and deterioration is accelerated. In order to prevent such deterioration, many products using an epoxy resin having excellent adhesion, chemical durability and mechanical strength have been used throughout the steel and concrete industries.

However, in areas with frequent vehicle traffic such as tunnels and piers, or where the frequency or concentration of other contaminants is relatively high compared to other areas, the concrete surface may be directly contaminated by soot or other contaminants, A problem of contamination by the secondary occurs.

The problem of contamination of the concrete surface has caused problems in terms of the appearance of the structure and environmental problems. Therefore, it is required to develop a technique for preventing the contamination of the surface of the concrete structure. Especially, in the case of a large structure, The necessity of prevention is more urgently required.

Korean Patent Publication No. 10-2003-0071231 Korean Patent No. 10-0943026 Korean Patent No. 10-1766286

Disclosure of the Invention The present invention has been made in view of the above problems, and it is an object of the present invention to provide a flame-retardant flame-retardant flame- And to provide a surface treatment method for protecting concrete or steel material for reinforcing pollution resistance using the same.

The present invention for achieving the object as described above (i) SiO ₂ - a urethane-inorganic composite resin of acryl, Al ₂ O ₃ - nano-silicate-phenoxy-inorganic composite resin, titanium dioxide, butyl acetate, first 100 parts by weight of a mixed substance including a solvent and a first additive, and (ii) 40 to 60 parts by weight of a mixed curing agent including a urethane resin, a second solvent and a second additive, Thereby providing a coating composition.

The present invention also provides a topcoat coating method for reinforcing stain resistance comprising coating and curing a topcoat coating layer or a steel primer layer on top of a concrete topcoat layer for reinforcing stain resistance according to various embodiments of the present invention.

According to the present invention, deterioration due to external factors is prevented, and excellent adhesion and air permeability are exhibited, as well as an effect of preventing the adhesion of contaminants, thereby greatly improving the stain resistance, antifouling property and flame retardancy of the concrete surface, The present invention can provide a hybrid coating composition capable of significantly improving the flame retardant performance so as to be applicable also to an underground structure such as an underground roadway or an underground structure such as a subway or a cavity or an interior of a hermetic structure and a surface treatment method for protecting concrete or steel material .

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view for explaining a method of repairing a concrete structure or a steel structure according to an embodiment of the present invention; FIG. The lower and upper views shown in Fig. 1 correspond to the lower and upper ends, respectively, used in the embodiment.
FIG. 2 is a process diagram of a tunnel underground vehicle road surface protection paint construction method according to an embodiment of the present invention.
FIG. 3 is a process diagram of a coating method according to an embodiment of the present invention.

In the following, various aspects and various embodiments of the present invention will be described in more detail.

One aspect of the present invention is (i) SiO ₂ - a urethane-acrylic organic-inorganic composite resin, Al ₂ O _{3-phenoxy-inorganic} composite resin, titanium dioxide, butyl acetate, a first solvent and a first additive nano-silicate And (ii) 40 to 60 parts by weight of a mixed curing agent including a urethane resin, a second solvent and a second additive. The present invention also relates to a composition for top coat coating for protecting concrete or steel material .

In place of the urethane resin, a silicone-modified urethane acrylate resin may be used. When a urethane resin is used, a water-soluble or aqueous urethane resin, a urethane dispersion, a water-dispersible urethane resin and the like may be used.

In one embodiment, the component (i) comprises 35 to 45% by weight of an inorganic complex resin of SiO ₂ -urethane-acrylic, 10 to 20% by weight of an Al ₂ O ₃ -nosilicate-phenoxy organic complex resin, 2 to 4% by weight of titanium, 2 to 4% by weight of butyl acetate, 20 to 30% by weight of the first solvent and 20 to 30% by weight of the second additive.

In another embodiment, the additive is selected from talcum, quencher, dispersant, defoamer, oxide black and mixtures of two or more thereof.

In another embodiment, the component (ii) comprises 35 to 45 wt% urethane resin, 25 to 35 wt% of the second solvent, and 25 to 35 wt% of the second additive.

In another embodiment, the second additive comprises methyl isobutyl ketone, butyl acetate, and cellulose sulphate.

In a most preferred embodiment, the component (i) comprises 35 to 45% by weight of an inorganic complex resin of SiO ₂ -urethane-acrylic, 10 to 20% by weight of an Al ₂ O ₃ -nosilicate-phenoxy organic complex resin, (2) is composed of 2 to 4% by weight of titanium dioxide, 2 to 4% by weight of butyl acetate, 20 to 30% by weight of a first solvent and 20 to 30% by weight of a second additive, 25 to 35% by weight of the second solvent, and 25 to 35% by weight of the second additive.

The inventors of the present invention derived the above embodiments through numerous experiments and numerous trial and error. When the components of (i) and (ii) and the composition ranges thereof are satisfied at the same time, the inventors of the present invention found that smoke toxicity, (I) and (ii) are missing or none of the composition ranges is satisfied, while the flame retarding properties such as the heat, the continuous heat, the smoke density and the oxygen index are all improved at the same time, Some of the flame retardant properties such as toxicity, flame propagation continuous heat, smoke density, and oxygen index could be improved, but not all of them were improved at the same time.

Another aspect of the present invention relates to a top coat coating method for reinforcing stain resistance comprising coating and curing a composition for top soil-strengthening top coat according to various embodiments of the present invention on a concrete undercoat layer or a steel primer layer .

In order to synthesize the urethane-acrylic resin used in the present invention, an urethane dispersion containing an acrylic monomer in the core can be synthesized by first introducing an acrylic monomer into the urethane resin. Thereafter, an initiator of an acrylic monomer is added, and an acrylic monomer is further polymerized at a temperature of 75 to 90 DEG C for 6 hours to synthesize a urethane-acrylic resin.

The acrylic monomer may be 2-hydroxyethyl methacrylate, acrylamide or a compound thereof. In addition, the acrylic monomer reacts with the residual isocyanate contained in the urethane resin to obtain a urethane-acrylic resin having a very high density by crosslinking the urethane and the acrylic resin with a urethane or urea bond rather than a urethane- have.

The content of the acrylic monomer is preferably 2 to 5% by weight, and if the content is less than 2% by weight, the amount of the monomer reacting with the residual isocyanate is small so that the degree of crosslinking of the urethane- The effect of the urethane reaction of the acrylic monomer and the isocyanate becomes insignificant, which is uneconomical.

In order to secure the hardness of the resin by controlling the composition ratio of the isocyanate constituting the hard segment, the equivalence ratio (equivalent ratio of NCO / OH) of the NCO group and the OH group at the time of polymerization of the urethane- . When the value of the equivalence ratio of NCO / OH is less than 1, the process blackening property is lowered. When the value of the equivalence ratio is more than 3, the solution stability and corrosion resistance are lowered. Further, in order to secure such an effect, the value of the NCO / OH equivalence ratio is more preferably controlled to 1.3 to 1.9, and most preferably to 1.6.

Unlike general phenoxy resins, the monomers used for the synthesis of the phenoxy resins may be alkyl-substituted phenols for improving the crosslinking of the resin and improving the physical properties. The alkyl-substituted phenol mohener may be at least one selected from among 4-ethylphenol, 2,6-dimethylphenol, 2-ethylphenol and 2-isopropylphenol.

The crosslinking agent is preferably hexamethylenetetramine, and the silicate is added together with the crosslinking agent, preferably 10 to 50% by weight based on the crosslinking agent. At this time, the particle size of the nanosilicate is preferably 20 nm or less, more preferably 10 to 20 nm. When the particle size is limited, it is possible to increase the density of the resin coating to improve the adhesion of the coating film during bending or the like.

On the other hand, the nanosilicate may be one selected from calcium silicate, lithium silicate and ammonium hexafluorosilicate.

The compositions for top coat coating according to various embodiments of the present invention can also be used in a transparent form, but can also include a dye, pigment, or other coloring material to provide a colored hypertitre coating Composition type can also be implemented.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the scope and content of the present invention can not be construed to be limited or limited by the following Examples. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the present invention as set forth in the following claims. It is natural that it belongs to the claims.

In addition, the experimental results presented below only show representative experimental results of the embodiments and the comparative examples, and the respective effects of various embodiments of the present invention which are not explicitly described below will be specifically described in the corresponding part.

Example

Production Example 1: Preparation of undercoating composition

(1) Preparation of a subject for a colored hybrid coating composition

By weight of an epoxy-silicone resin, 0.5% by weight of a polyester derivative, 1.1% by weight of an organopolysiloxane, 1.1% by weight of a thickener, 26% by weight of barium sulfate, 2.5% by weight of titanium dioxide, 3% 3.8% by weight of orthophosphate were mixed and milled to obtain a slurry having a particle size of 15 m. To the obtained slurry was added 18% by weight of an epoxy-silicone resin, 1.5% by weight of a light stabilizer and 13.5% by weight of a 45% Were mixed using a stirrer to prepare a subject for a colored hybrid coating composition.

(2) Preparation of transparent hybrid coating composition

100 parts by weight of a subject and 20 parts by weight of a curing agent were mixed at room temperature, and then 3 parts by weight of a functional additive were mixed at 40 DEG C to prepare a transparent hybrid coating composition. The composition of each component is shown in Table 1 below. Each content means weight%.

Manufacturing example  2: Lower coating

To remove foreign matter (oil, dirt, etc.) on the concrete surface, a solution of 2 to 3 wt% hydrochloric acid was sprayed, followed by washing with water and drying. In the case of repairing and reinforcing concrete structures subjected to deterioration, they were washed with high pressure and sufficiently dried. If there is an excited portion of the concrete surface, the excavated portion is removed, and the surface of the damaged portion or uneven portion is smoothed with mortar. In the case of repair and reinforcement of concrete structures, if the crack width on the concrete surface is 2 mm or more, cut into V shape and then fill and repair with mortar. The empty spaces and joints were also filled and repaired with mortar, and then the repair work was smoothed.

Then, the composition for undercoating prepared in Preparation Example 1 was stirred and mixed with a stirrer or the like, and then applied to the surface of the concrete. At this time, the mixed raw material was left to stand for a long time, and physical properties were changed. Thus, the application was completed within about 1 hour (pot life) after mixing. The coating of the undercoating material was carried out using a spray gun (undercoat thickness: about 80 袖 m), but after about 6 hours at the standard state (room temperature 1 atm) after application as occasion demands, ), And then apply second coating.

Example 1: Preparation of Top Coating Composition

(1) Production of first organic-inorganic hybrid resin

Inorganic hybrid resin was prepared by chemically substituting inorganic nano-particles for the terminal substituent of the organic resin. The organic resin used was a urethane-acrylic resin (weight average molecular weight: 15,000, softening point: 80 캜), and an urethane resin was charged with an acrylic monomer mixed with 2-hydroxyethyl methacrylate and acrylamide in a weight ratio of 1: 1 And then synthesized. The inorganic nanoparticles used were SiO ₂ (average particle diameter: 7 μm). Was prepared in the presence or absence of the acrylic-based composite resin were mixed so that 1, using phosphoric acid as catalyst SiO ₂ by reacting substituted-urethane: specifically organic resin: The weight ratio of the inorganic nano-particles 9.

(2) Production of second organic-inorganic hybrid resin

And are the same as in Preparation Example 1 except that use: (10μm average particle size) (:: 7000 softening point 70 ℃ weight average molecular weight) and Al ₂ O ₃ polyurethane-phenoxy resin-acrylic resin and the nano-silicate, instead of SiO ₂ To prepare an Al ₂ O ₃ -nonosilicate-phenoxy organic complex resin.

(3) Preparation of Top Coating Composition for Stain Resistance Contamination

Using the first and second organic-inorganic hybrid resin prepared above, a base and a curing agent were prepared in the compositions shown in Table 2 below. 100 parts by weight of a subject and 50 parts by weight of a curing agent were mixed to prepare a top coat composition for improving stain resistance. Each content in Table 2 means weight%.

Example  2: Top Coating

After the application of the undercoating composition, it was performed after confirming the undercoating operation state and the dry hardening state after about 8 hours under the standard condition. The above topcoat was applied using a spray gun (top coat thickness: about 70 탆), but after about 6 hours under the standard condition after the first coating, after confirming the drying condition (solidification drying) If it is necessary to further strengthen the applied surface, it can be applied more than three times.

Comparative Example 1

Except that the urethane-acrylic resin (weight average molecular weight: 15,000, softening point: 80 占 폚) used as a raw material for the production of composite resin in Production Example 1 was used in the same composition instead of the first organic-inorganic hybrid resin prepared in Production Example 1 And the upper coating was carried out in the same manner as in Examples 1 and 2 above.

Comparative Example 2

Phenoxy resin (weight average molecular weight: 7,000, softening point: 70 ° C) used as a raw material for producing a composite resin in Production Example 2 was used in the same composition instead of the first organic-inorganic hybrid resin prepared in Preparation Example 1 The upper coating was carried out in the same manner as in Examples 1 and 2 above.

Comparative Example 3

The top coating was carried out in the same manner as in Examples 1 and 2 except that the commercially available modified acrylic resin was used in the same composition instead of the first organic-inorganic hybrid resin prepared in Preparation Example 1.

Comparative Example 4

The top coat was carried out in the same manner as in Examples 1 and 2 except that the commercially available modified polyester resin was used in the same composition instead of the second organic-inorganic hybrid resin prepared in Preparation Example 2.

Test examples and comparative test examples 1 to 4

In order to ensure that all the properties of the undercoat material and the topcoat material can be exhibited, the primer and the topcoat material were cured for 7 days under the standard condition after the completion of the above-mentioned application of the primer and the topcoat material.

The promoting stainability was evaluated by spraying carbon black dispersed in 20% by weight of water and solvent (mineral spirits) on the top surface of concrete, dipping at 80 ° C for 5 hours, drying and rinsability. The water washability was evaluated by visually checking the remaining state after the water was washed naturally by running the surface with carbon on flowing water. The rubbing property was visually judged by the degree of surface wiping when the surface of the film was wiped with gauze or a toilet paper

Antifouling (Magic Pollutant) Test The stain resistance of the coated surface of the concrete was evaluated according to the standards and procedures set forth in RSM 0030.

As a result, the surface of the concrete on the concrete according to Examples 1 and 2 was in a very good condition such that the water washability of the water, the water washability of the solvent, the rubbing property of the water, the rubbing property of the solvent and the antifouling property (magic staining property) Respectively.

On the other hand, the surface of the concrete on the concrete according to Comparative Examples 1 to 4 exhibits traces clearly distinguishable by ① scratching property of solvent, ② antifouling property, ③ water washing property of solvent, and ④ antifouling property, The concrete topcoats according to Examples 1 and 2 were found to be poorer than the coated surface.

Table 3 shows the results of evaluating the properties of the top coating films according to the above Examples 1 and 2 as concrete covering materials for concrete protection and Table 4 shows the evaluation results of the quality performance This is a result.

Claims (7)

(i) a mixed substrate 100 comprising an organic-inorganic composite resin of SiO ₂ -urethane-acrylic, Al ₂ O ₃ -nonosilicate-phenoxy organic complex resin, titanium dioxide, butyl acetate, a first solvent and a first additive And (ii) 40 to 60 parts by weight of a curing agent mixed with a urethane resin, a second solvent and a second additive. The method according to claim 1, wherein the component (i) comprises 35 to 45% by weight of an organic-inorganic hybrid resin of SiO ₂ -urethane-acryl, 10 to 20% by weight of an Al ₂ O ₃ -nosilicate- A composition for top coat protection for concrete or steel material, which comprises 2 to 4% by weight of titanium, 2 to 4% by weight of butyl acetate, 20 to 30% by weight of a first solvent and 20 to 30% by weight of a first additive. . The composition according to claim 2, wherein the additive is selected from talc, a quencher, a dispersant, an antifoaming agent, an oxide black, and a mixture of two or more thereof. The concrete according to claim 1, wherein the component (ii) comprises 35 to 45% by weight of a urethane resin, 25 to 35% by weight of a second solvent and 25 to 35% by weight of a second additive Compositions for top coat coating for steel protection. 5. The composition of claim 4, wherein the second additive comprises methyl isobutyl ketone, butyl acetate, and cellulose sulphate. The method according to claim 1, wherein the component (i) comprises 35 to 45% by weight of an organic-inorganic hybrid resin of SiO ₂ -urethane-acryl, 10 to 20% by weight of an Al ₂ O ₃ -nosilicate- 2 to 4% by weight of titanium, 2 to 4% by weight of butyl acetate, 20 to 30% by weight of a first solvent and 20 to 30% by weight of a first additive,
(Ii) is composed of 35 to 45% by weight of a urethane resin, 25 to 35% by weight of a second solvent, and 25 to 35% by weight of a second additive. (A) a step of coating a concrete primer coating layer or a steel primer layer with a composition for coating a concrete top coat according to any one of claims 1 to 5 and curing the coating composition for stain resistance in a concrete or steel material Coating method.

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