KR102482981B1 - Paint composition containing specific compound and process for forming a durable coating layer using the same - Google Patents

Abstract

The present invention relates to a paint composition for corrosion prevention and durability enhancement of a structure, comprising: a powder mixture consisting of 0.8% by weight of zinc, 0.06 to 0.11% by weight of phosphorus and the balance of aluminum (Al); and an adhesive resin in which the powder mixture is uniformly dispersed, wherein the adhesive resin further includes 0.1 to 0.2 parts by weight of a compound represented by chemical formula 1, and 0.1 to 0.2 parts by weight of a compound represented by chemical formula 2, and 0.1 to 0.2 parts by weight of a compound represented by chemical formula 3, respectively, based on 100 parts by weight of the adhesive resin.

Description

Paint composition containing specific compound and process for forming a durable coating layer using the same}

The present invention relates to a coating composition for preventing corrosion and enhancing durability of a steel structure or concrete structure and a film bonding method using the same, and more particularly, to a coating composition that can be simply applied at room temperature and uniformly forms a corrosion-resistant film with excellent physical properties. It relates to a coating composition that can be used and a film adhesion method using the same.

In general, steel structures or concrete structures are mostly exposed to corrosive environments such as moisture and air, and thus, a method of anticorrosive treatment of the surface is used to prevent corrosion.

For example, a method of forming a film on the surface of a steel structure or concrete structure by using an epoxy-based, vinyl ester-based, fluororesin-based, acrylic rubber-based, or chlorinated rubber-based paint has been developed. However, since these are organic paints, they have excellent initial performance, but show differences in deformation characteristics such as thermal expansion coefficient and elongation from structures. Therefore, there is a problem in that the formed film is detached from the structure over time and the adhesive strength is lowered.

In order to solve this problem, the present applicant proposed an aluminum oxide film bonding method using a paint composition containing a metal mixture powder containing aluminum as a main material and adding metal components such as chromium and nickel (Refer to Korean Patent No. 10-0503561) . When the coating composition containing the metal mixture powder is used, a corrosion-resistant aluminum film having excellent physical properties such as adhesion strength and elongation can be formed. However, the coating composition with the addition of chromium and nickel as sub-materials has good strength but a large weight, which contributes to sagging and flow of the coating film over time during film formation.

Therefore, there is a continuing demand for a composition with further improved adhesive strength while improving the deflection of the film over time.

A technical problem to be achieved by the present invention is to solve the above problems, and to provide a coating composition with improved durability by further improving adhesive strength while improving film sagging over time.

Another technical problem to be achieved by the present invention is to provide a film adhesion method using the coating composition.

In order to solve the above technical problem, according to the present invention, a powder mixture consisting of 0.8% by weight of zinc, 0.06 to 0.11% by weight of phosphorus, and the remaining amount of aluminum (Al); And an adhesive resin in which the powder mixture is uniformly dispersed; a coating composition for preventing corrosion and enhancing durability of a structure,

The adhesive resin is based on 100 parts by weight of the adhesive resin

0.1 to 0.2 parts by weight of a compound represented by Formula 1 below;

0.1 to 0.2 parts by weight of a compound represented by Formula 2 below, and

0.1 to 0.2 parts by weight of a compound represented by Formula 3 below.

<Formula 1>

<Formula 2>

<Formula 3>

In the paint composition of the present invention, the adhesive resin may further include 0.05 to 0.1 parts by weight of a compound represented by Formula 4 based on 100 parts by weight of the adhesive resin.

<Formula 4>

In order to achieve the above other technical problem, the film bonding method of the present invention,

(a) preparing a powder mixture consisting of 0.8% by weight of zinc (Zn), 0.06 to 0.11% by weight of phosphorus, and the balance of aluminum (Al); and

(b) 0.1 to 0.2 parts by weight of a compound represented by Formula 1, 0.1 to 0.2 parts by weight of a compound represented by Formula 2, and Formula 3 below, based on 100 parts by weight of an adhesive resin and the adhesive resin. and uniformly dispersing 0.1 to 0.2 parts by weight of the indicated compound in the further mixed composite adhesive resin and spraying it on the surface of the structure to form a film.

<Formula 1>

<Formula 2>

<Formula 3>

In the film bonding method of the present invention, based on 100 parts by weight of the adhesive resin, 0.05 to 0.1 parts by weight of the compound represented by Formula 4 may be further mixed with the composite adhesive resin.

<Formula 4>

When forming a film on the surface of a structure such as a steel material using the coating composition according to the present invention, the adhesion strength is improved, the physical properties such as bending resistance are good, and the sagging property of the film is also improved, so it can be effectively used for protection of structures.

Hereinafter, the present invention will be described in detail. Prior to this, the terms or words used in this specification and claims should not be construed as being limited to the usual or dictionary meaning, and the inventor appropriately uses the concept of the term in order to explain his/her invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined.

The coating composition according to the present invention is a powder mixture consisting of 0.8% by weight of zinc, 0.06 to 0.11% by weight of phosphorus and the balance of aluminum (Al); And an adhesive resin in which the powder mixture is uniformly dispersed. As a coating composition for preventing corrosion and enhancing durability of structures,

The adhesive resin is based on 100 parts by weight of the adhesive resin

0.1 to 0.2 parts by weight of a compound represented by Formula 1 below;

0.1 to 0.2 parts by weight of a compound represented by Formula 2 below, and

0.1 to 0.2 parts by weight of a compound represented by Formula 3 below.

<Formula 1>

<Formula 2>

<Formula 3>

As is already known, aluminum, which is the main component of the powder mixture dispersed in the adhesive resin, is rapidly oxidized to form an aluminum oxide (Al ₂ O ₃ ) film. The aluminum oxide film blocks contact with the external environment, such as oxygen or moisture, that can corrode steel or concrete structures.

0.8% by weight of the zinc component mixed with the aluminum powder contributes to the improvement of the wear resistance and weather resistance of the film.

In addition, the powder mixture of the present invention contains 0.06 to 0.11% by weight of phosphorus (P), and the added phosphorus helps to uniformly disperse the above-mentioned metal powders in the adhesive resin, and also improves the uniformity and durability of the aluminum oxide film. function to improve.

The powder mixtures described above are mixed with an appropriate adhesive resin to be adhered to the surface of the structure, uniformly dispersed, and then sprayed and applied. Such an adhesive resin may be used by adjusting the viscosity according to the application method, and it is well known to use a polyurethane resin or an epoxy resin having excellent adhesiveness and elasticity. In particular, the polyurethane resin has excellent permeation inhibition performance for chloride and carbon dioxide gas, and also has good chemical resistance and permeability resistance to moisture and oxygen. In addition, other adhesive resin components such as formaldehyde resin and ethylene vinyl acetate copolymer resin may be further included.

In the coating composition of the present invention, the adhesive resin is 0.1 to 0.2 parts by weight of the compound represented by Formula 1, 0.1 to 0.2 parts by weight of the compound represented by Formula 2, and the compound represented by Formula 3, based on 100 parts by weight of the adhesive resin. It further includes 0.1 to 0.2 parts by weight of the compound to be.

The compounds represented by Formulas 1 and 2 have rigid chemical structures, and these compounds are hardened by a curing reaction by artificial or sunlight ultraviolet rays, so that not only the adhesive strength of the film increases, but also the sagging of the film. Improved. In addition, the compound represented by Formula 3 further improves the strength of the repair layer.

In the coating composition of the present invention, the adhesive resin preferably further comprises 0.05 to 0.1 parts by weight of a compound represented by Formula 4 based on 100 parts by weight of the adhesive resin to further enhance the function of the above-mentioned compound.

<Formula 4>

In addition, in the coating composition of the present invention, when the adhesive resin further includes 0.05 to 0.1 parts by weight of a compound represented by Formula 5 based on 100 parts by weight of the adhesive resin, the above effect can be further increased.

<Formula 5>

The compounds represented by Chemical Formulas 4 and 5 also have rigid chemical structures, and these compounds are hardened by a hardening reaction caused by artificial ultraviolet light or ultraviolet light of sunlight, especially on the surface of the repair layer. When used in combination with a compound, it contributes to increasing the adhesive strength of the coating and improving the sagging of the coating.

In particular, since the compound represented by Chemical Formula 5 has an H-type rigid chemical structure, the aforementioned effect can be further enhanced.

The film bonding method of the present invention,

(a) preparing a powder mixture consisting of 0.8% by weight of zinc (Zn), 0.06 to 0.11% by weight of phosphorus, and the balance of aluminum (Al); and

(b) the prepared powder mixture, 0.1 to 0.2 parts by weight of the compound represented by Formula 1, 0.1 to 0.2 parts by weight of the compound represented by Formula 2, and the above Formula 3 based on 100 parts by weight of the adhesive resin and the adhesive resin. and uniformly dispersing 0.1 to 0.2 parts by weight of the indicated compound in the further mixed composite adhesive resin and spraying it on the surface of the structure to form a film.

The composite adhesive resin may further mix 0.05 to 0.1 parts by weight of the compound represented by Chemical Formula 4 based on 100 parts by weight of the adhesive resin, and 0.05 to 0.1 parts by weight of the compound represented by Chemical Formula 5 based on 100 parts by weight of the adhesive resin. Wealth may be further included.

The mixing ratio of the powder mixture and the composite adhesive resin is preferably about 0.2:10 to 3:10. When spraying a coating solution dispersed and dissolved in an appropriate solvent for coating spraying, it is dried and cured naturally at room temperature in the air to form a coating, which is very simple. and can be built economically. After forming the film, the compounds represented by the formula may be cured using an ultraviolet ray generator, but may be gradually cured by ultraviolet rays included in sunlight.

The formed film is preferably formed to a thickness of 100 μm or less based on one application. If necessary, it is formed by laminating such a film layer several times, or a film layer formed of the coating composition according to the present invention and a conventional adhesive resin or A stronger coating layer can be formed by alternately forming coating layers made of only the composite adhesive resin of the present invention several times.

The film formed by this method has improved adhesion strength, good physical properties such as bending resistance, and improved sagging property of the film. In addition, it can show excellent protection against penetration of chloride ions, sulfurous acid gas, moisture, oxygen, etc., which are causes of corrosion of steel or concrete structures.

Hereinafter, examples will be described in detail to explain the present invention in detail. However, the embodiments according to the present invention can be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

[Synthesis of Formula 1 Compound]

The following compounds were synthesized by the methods shown below.

10.08 g (45.4 mmol) of 4-hydroxycinnamic acid tertbutyl (1-c-43a), 100 ml of N,N-dimethylformamide, and 9.4 g of potassium carbonate were added to a 300 ml four-neck flask, and the mixture was stirred for 10 minutes. In this mixture, 10.1 g (53 mmol) of 6-chlorohexyl acrylate was added, and the mixture was stirred at 90°C for 6 hours. The reaction mixture was cooled to 10°C, 100 ml of water was added, and the mixture was stirred for 1 hour. The mixture was filtered to obtain the crude product as a solid. This solid was dissolved in 25 ml of acetone, dropped into 45 ml of methanol, and cooled to 0°C. The generated solid was filtered, dissolved again in 12 ml of acetone, added dropwise into 25 ml of hexane, and cooled to 0°C. By filtering and drying the obtained solid, 8.56 g of compound 1-1 was obtained (yield 50%).

8.5 g of compound 1-1 and 22 ml of dichloromethane were added to a 200 ml three-necked flask and stirred. 22 ml of formic acid was dripped into this mixture, and it stirred at 40 degreeC for 5 hours. The reaction mixture was cooled to 30 degrees or less, and 50 ml of dichloromethane was added. The organic layer was separated and washed 4 times with 70 ml of water and once with 70 ml of saturated brine. The resulting solution was dried over sodium sulfate. After filtering out sodium sulfate, the solvent was distilled off. 10 ml of hexane and 4 ml of toluene were added to the obtained solid, and it stirred at room temperature for 30 minutes. By filtering and drying this mixture, 6.30 g of compound 1-2 was obtained (yield 87%).

1.31 g of 2,5-dihydroxybenzaldehyde, 25 ml of dichloromethane, 6.05 g of compound 1-2, and 0.07 g of N,N-dimethylaminopyridine were added to a 100 ml three-necked flask, and the mixture was stirred at 5°C for 10 minutes. In this mixture, 2.98 g of N,N-diisopropylcarbodiimide was added dropwise while maintaining the temperature at 10 degrees or less, and the mixture was stirred at 30°C for 6 hours. After adding 0.08 ml of water to the reaction mixture, the solid was removed by filtration. After passing the obtained solution through a column (silica gel + alumina, dichloromethane), the solvent was distilled off. The obtained solid was dissolved in 10 ml of acetone, added dropwise into 30 ml of methanol, and cooled to 0°C. By filtering and drying the obtained solid, 4.80g of compounds 1-3 were obtained (yield 69%).

4.8 g of compounds 1-3, 1.07 g of 2-hydrazinobenzothiazole, and 20 ml of tetrahydrofuran were added to a 100 ml three-necked flask, and the mixture was stirred at 50°C for 15 hours. The reaction mixture was cooled to room temperature, and the precipitated solid was filtered. The obtained solid was purified by silica gel column chromatography (dichloromethane/ethyl acetate = 10/1). 2.40g of the compound of Formula 1 was obtained by filtering and drying the solution after passing through a column.

¹ H NMR (CDCl ₃ )δ: 1.41-1.61 (p, 8H), 1.65-1.80 (p, 4H), 1.7 (br, 1H), 1.80-1.97 (p, 4H), 4.02 (t, 2H), 4.17(t, 2H), 5.82(d, 2H), 6.10-6.18(dd, 2H), 6.39-6.44(s+d, 3H), 6.93(dd, 4H), 7.09(t, 2H), 7.23( s, 1H), 7.30 (d, 1H), 7.43 (d, 1H), 7.50-7.58 (p, 4H), 7.75-7.89 (p, 3H), 8.10 (s, 1H).

LC-MS: m/z 885.61 [M+]

[Synthesis of Formula 2 Compound]

The following compounds were synthesized by the methods shown below.

The following compounds were synthesized by the methods shown below.

,

탄산칼륨, 에탄올, 테트라키스(트리페닐포스핀)팔라듐(0)을 더하고 가열 교반했다. 통상의 후처리를 행한 후, 칼럼 크로마토그래피 및 재결정에 의해 정제를 행하여,

의 화합물 2-1을 얻었다.in the reaction vessel

,

Potassium carbonate, ethanol, and tetrakis(triphenylphosphine)palladium(0) were added and heated and stirred. After performing a normal post-treatment, purification is performed by column chromatography and recrystallization,

of Compound 2-1 was obtained.

,

, N,N-디메틸아미노피리딘, 디클로로메탄을 더했다. 이어서 디이소프로필카르보디이미드를 더하고 교반했다. 통상의 후처리를 행한 후, 칼럼 크로마토그래피 및 재결정에 의해 정제를 행하여,

으로 표시되는 화합물 2-2를 얻었다.in the reaction vessel

,

, N,N-dimethylaminopyridine and dichloromethane were added. Then, diisopropyl carbodiimide was added and stirred. After performing a normal post-treatment, purification is performed by column chromatography and recrystallization,

Compound 2-2 represented by was obtained.

Compounds 2-1 and 2-2, hydrazine monohydrate, and ethanol were added to the reaction vessel, followed by heating and stirring. After carrying out normal post-treatment, purification was performed by column chromatography to obtain a compound represented by formula (2).

MS(m/z):853[M++1]

[Synthesis of Formula 3 Compound]

The following compounds were synthesized by the methods shown below.

Phosphoryl trichloride (1.27 g, 8.3 mmol) was slowly added dropwise to 10 ml of DMF at 0 °C under a nitrogen atmosphere, followed by stirring for 1 hour. Thieno[2,3-d]thiazol-2-amine (1 g, 6.4 mmol) was added thereto, and the mixture was heated to 80 °C and stirred to proceed with the reaction. Then, the temperature was lowered to room temperature, and the reaction was terminated by adding 30 ml of water. 30 ml of 1N NaOH was added to the resulting solid, and then 50 ml of chloroform was added to dissolve it. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and E?K acetate to prepare a solid intermediate 3-1 (0.91g, 77%, MS: [M+H]+ = 184.0).

At 0 °C, intermediate 3-1 (1 g, 5.4 mmol) was added to 3 ml of acetic acid and 7 ml of propionic acid, followed by stirring for 30 minutes. After dissolving sodium nitrite (0.39 g, 5.7 mmol) in 16 ml of sulfuric acid, it was slowly added dropwise and stirred for 30 minutes while maintaining below 5 °C. After slowly adding N,N-diethylaniline (1.2 g, 8.1 mmol) dissolved in 5 ml of methanol dropwise, the mixture was stirred for 2 hours. At this time, the pH was titrated to be maintained between 5-7 with a 2N sodium acetate aqueous solution. After completion of the reaction, the mixture was filtered and washed twice with water and methanol to obtain solid intermediate 3-2 (1.4 g, 75%, MS: [M+H]+ = 345.1).

Intermediate 3-2 (0.5 g, 1.5 mmol) and 2-(4-butoxyphenyl)acetonitrile (0.33 g, 1.7 mmol) were dissolved in 10 ml of ethanol. After adding 5 mol% of piperidine to the mixture solution, it was refluxed for 2 hours. After lowering the temperature of the reaction mixture to room temperature, the resulting solid was extracted three times using 20 ml of chloroform and 20 ml of water. After removing water with magnesium sulfate and evaporating the solvent, the compound of formula 3 (0.45 g, 60%, MS: [M+H]+ = 515.3) was purified through a silica column using chloroform and ethyl K acetate. was manufactured.

[Synthesis of Formula 4 Compound]

The following compounds were synthesized by the methods shown below.

4-Bromobenzoic acid (50 g), tert-butyl alcohol (20.3 g), and dimethylaminopyridine (12.2 g) were dissolved in dichloromethane, and diisopropylcarbodiimide (DIC, 37.7 g) was added dropwise at 35°C. , and stirred for 5 hours. The reaction liquid was filtered, and the filtrate was concentrated. The solid was purified by column chromatography to obtain compound 4-1 (49 g).

Compound 4-1 (49 g) was dissolved in NMP, and potassium carbonate (34.2 g) and ethyl acrylate (24.8 g) were added. Nitrogen substitution was performed, palladium acetate (0.43 g) was added, and the mixture was heated and stirred at 110°C. After stirring for 4 hours, water (300 ml) was added, and ethyl acetate extracted. The organic layer was washed with 1% hydrochloric acid and brine. It was dehydrated with sodium sulfate, and the organic layer was concentrated. The obtained compound was dissolved in 100 ml of ethanol, and potassium hydroxide (15.2 g), 50 ml of ethanol, and 50 ml of water were added. After stirring at room temperature for 5 hours, 100 ml of water was added and neutralized with hydrochloric acid. The aqueous layer was extracted with ethyl acetate and concentrated to obtain an oily solid (Compound 4-2, 14.7 g).

The obtained compound 4-2 was dissolved in dichloromethane, and DMAP (2.90 g), 4-hydroxybutyl acrylate (10.3 g), and DMF 400 ml were added. DIC (9.0 g) was slowly added dropwise at room temperature, and the mixture was stirred for 24 hours. Washed with water and extracted with dichloromethane. It was purified by silica gel column chromatography. Formic acid was added to the obtained oily compound, and the mixture was stirred at room temperature for 9 hours and at 45°C for 4 hours. After adding 100 ml of water to the reaction system and neutralizing with sodium hydroxide, extraction was performed with ethyl acetate. The organic layer was concentrated and dried to obtain compound 4-3 (6.5 g).

Compound 4-3 (6.5 g) was dissolved in 200 ml of dichloromethane, and DMAP (0.6 g) and dihydroxybenzaldehyde (1.2 g) were added. DIC (2.5 g) was added dropwise at room temperature and stirred for 10 hours. The reaction liquid was filtered, and the organic layer was concentrated. Purification was performed by silica gel column chromatography to obtain compound 4-4 (5 g).

Compound 4-4 (5 g) was dissolved in 50 ml of ethanol, a benzothiazolehydrazine derivative was added, and the mixture was stirred at 45°C for 5 hours. When cooled to room temperature, solid precipitated and was collected by filtration. It was purified by recrystallization to obtain 3.5 g of a compound represented by the formula (4).

[Synthesis of Compound of Formula 5]

The following compounds were synthesized by the methods shown below.

, 트리에틸아민, 디클로로메탄, 숙신산클로리드를 더하고 교반했다. 통상의 후처리를 행한 후, 칼럼 크로마토그래피 및 재결정에 의해 정제를 행하여, 화합물 5-1을 얻었다.in the reaction vessel

, triethylamine, dichloromethane, and succinic acid chloride were added and stirred. After performing normal post-treatment, purification was performed by column chromatography and recrystallization to obtain compound 5-1.

Compound 5-1 and dichloromethane were added to the reaction vessel. While cooling to -78°C, boron tribromide was added and stirred. After carrying out normal post-treatment, purification was performed by column chromatography and recrystallization to obtain compound 5-2.

, N,N-디메틸아미노피리딘, 디클로로메탄을 더했다. 디이소프로필카르보디이미드를 더하고 교반했다. 통상의 후처리를 행한 후, 칼럼 크로마토그래피 및 재결정에 의해 정제를 행하여, 화학식 5의 화합물을 얻었다.compound 5-2 to the reaction vessel;

, N,N-dimethylaminopyridine and dichloromethane were added. Diisopropylcarbodiimide was added and stirred. After performing usual post-treatment, purification was performed by column chromatography and recrystallization to obtain a compound of formula (5).

MS(m/z): 1543[M++1]

<Example 1>

A powder mixture composed of 0.8% by weight of zinc, 0.1% by weight of phosphorus, and the balance of aluminum, an adhesive resin made of a polyurethane resin, and the compounds represented by Formulas 1, 2, and 3 synthesized above based on 100 parts by weight of the adhesive resin. A composite resin containing 0.15 parts by weight of each and 0.0015 parts by weight of photopolymerization initiator Irgacure907 (manufactured by BASF) was mixed at a ratio of 1:10, dispersed and dissolved in a solvent, and then applied by spraying to the steel surface by spraying, at room temperature for a predetermined time. After leaving it to form a 35 μm thick film according to this method, it was dried and cured naturally at room temperature.

Subsequently, ultraviolet rays were irradiated at an intensity of 40 mW/cm 2 for 20 minutes using a high-pressure mercury lamp, and various physical properties were evaluated according to the quality standard test described below.

<Example 2>

It was prepared in the same manner as in Example 1, except that the compound of Formula 4 synthesized by the above method was further mixed in an amount of 0.08 parts by weight based on 100 parts by weight of the adhesive resin.

<Example 3>

The compound of Formula 5 synthesized by the above method was further mixed in an amount of 0.08 parts by weight based on 100 parts by weight of the adhesive resin, dried to prepare a repair material composition, and then tested in the same manner as in Example 2, except that the construction test was performed. .

Comparative Example 1

As a comparative example, the composition described in Korean Patent No. 10-0503561 of the present applicant was used.

A powder mixture consisting of 0.3% by weight of zinc, 0.5% by weight of chromium, 0.7% by weight of nickel, 0.1% by weight of phosphorus, and 97.8% by weight of aluminum was mixed with a polyurethane resin at a ratio of 1:10, dispersed and dissolved in a solvent, and then tested. It was applied by spraying on the surface of the target material and left at room temperature for a predetermined time to form a film with a thickness of 35 μm.

Measurement of film adhesion strength

In order to confirm the adhesion strength of the films formed according to Examples 1-3 and Comparative Example 1, the following tests were conducted.

After forming the aluminum oxide film of Example 1 according to the method described above on the steel structure, the steel attachment was attached and measured by applying a tensile force using an adhesion tester according to KS F 4715-01 and JIS A 6910 standards.

The film adhesive strength of Example 1 was 46 kgf/cm ² , the film adhesive strength of Example 2 was 48 kgf/cm ² , the film adhesive strength of Example 3 was 49 kgf/cm ² and the film adhesive strength of Comparative Example 1 was 35 kgf/cm 2 . Appeared to be about ² cm.

Claims (4)

A powder mixture consisting of 0.8% by weight of zinc, 0.06 to 0.11% by weight of phosphorus and the balance of aluminum (Al); and
In the coating composition for preventing corrosion and enhancing durability of structures, consisting of an adhesive resin in which the powder mixture is uniformly dispersed,
The adhesive resin is based on 100 parts by weight of the adhesive resin
0.1 to 0.2 parts by weight of a compound represented by Formula 1 below;
0.1 to 0.2 parts by weight of a compound represented by Formula 2 below, and
A coating composition comprising 0.1 to 0.2 parts by weight of a compound represented by Formula 3 below:
<Formula 1>

<Formula 2>

<Formula 3>

According to claim 1,
The coating composition characterized in that the adhesive resin further comprises 0.05 to 0.1 parts by weight of a compound represented by Formula 4 based on 100 parts by weight of the adhesive resin:
<Formula 4>

(a) preparing a powder mixture consisting of 0.8% by weight of zinc (Zn), 0.06 to 0.11% by weight of phosphorus, and the balance of aluminum (Al); and
(b) 0.1 to 0.2 parts by weight of a compound represented by Formula 1, 0.1 to 0.2 parts by weight of a compound represented by Formula 2, and Formula 3 below, based on 100 parts by weight of an adhesive resin and the adhesive resin. Forming a film by uniformly dispersing 0.1 to 0.2 parts by weight of the indicated compound in a further mixed composite adhesive resin and spraying it on the surface of the structure; a film bonding method comprising:
<Formula 1>

<Formula 2>

<Formula 3>

According to claim 3,
The composite adhesive resin is a film bonding method characterized by further mixing 0.05 to 0.1 parts by weight of a compound represented by the following formula (4) based on 100 parts by weight of the adhesive resin:
<Formula 4>