KR102638275B1 - Paint composition improving curtaining properties and process for forming a coating layer for preventing corrosion and improving water repellency - Google Patents

Abstract

The present invention provides 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, wherein the adhesive resin is a polyurethane resin and includes a compound represented by Formula 1, a compound represented by Formula 2, and Formula 3 based on 100 parts by weight of the adhesive resin. It is characterized in that it further contains 0.1 to 0.2 parts by weight of each compound represented by .

Description

Paint composition with improved sagging properties and waterproofing and anti-corrosion film adhesion method using the same {Paint composition improving curtaining properties and process for forming a coating layer for preventing corrosion and improving water repellency}

The present invention relates to a coating composition for preventing corrosion and improving the durability of steel structures or concrete structures, and to a waterproofing and anti-corrosion film adhesion method using the same. More specifically, it relates to a corrosion-resistant film that can be easily installed even at room temperature and has excellent physical properties. It relates to a paint composition that can be formed uniformly and a waterproofing and anti-corrosion film adhesion method using the same.

In general, most steel structures and concrete structures are exposed to corrosive environments such as moisture and air, so a method of treating the surface with anti-corrosion treatment is used to prevent corrosion.

For example, a method of forming a film on the surface of a steel structure or concrete structure using epoxy-based, vinyl ester-based, fluoropolymer-based, acrylic rubber-based, chlorinated rubber-based paints has been developed. However, since these are organic paints, their initial performance is excellent, but their deformation characteristics, such as thermal expansion coefficient and elongation, are different from those of the structure. Therefore, there is a problem that the formed film falls off from the structure over time and the adhesive strength deteriorates.

To solve this problem, the present applicant proposed an aluminum oxide film adhesion method using a paint composition containing metal mixture powder as the main material and adding metal components such as chromium and nickel and using aluminum as the main material (see Korean Patent No. 10-0503561). . Using the coating composition containing the metal mixture powder, a corrosion-resistant aluminum film with excellent physical properties such as adhesion strength and extensibility can be formed. However, paint compositions containing additives such as chromium and nickel have good strength but are heavy and have the problem of contributing to the sagging and flow phenomenon of the coating film over time during film formation.

Accordingly, there continues to be a demand for a composition that further improves adhesive strength while improving the sagging of the film over time.

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

Another technical problem to be achieved by the present invention is to provide a waterproofing and anti-corrosion film adhesion method using the above paint 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. The paint composition with improved sagging properties consists of,

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

0.1 to 0.2 parts by weight of a compound represented by the following formula (1),

0.1 to 0.2 parts by weight of a compound represented by the following formula (2) and

It contains 0.1 to 0.2 parts by weight of a compound represented by the following formula (3).

<Formula 1>

<Formula 2>

<Formula 3>

In the coating composition of the present invention, the adhesive resin may further include 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>

In order to achieve the above other technical problems, the waterproofing and anti-corrosion film adhesion method of the present invention is,

(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 remaining amount of aluminum (Al); and

(b) The prepared powder mixture is mixed with an adhesive resin and 0.1 to 0.2 parts by weight of a compound represented by the following formula (1), 0.1 to 0.2 parts by weight of a compound represented by the following formula (2), and the following formula (3) based on 100 parts by weight of the adhesive resin. It includes the step of 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 to form a film.

<Formula 1>

<Formula 2>

<Formula 3>

In the waterproof and anti-corrosive film adhesion method of the present invention, based on 100 parts by weight of the adhesive resin, 0.05 to 0.1 parts by weight of a compound represented by the following formula (4) may be further mixed with the composite adhesive resin.

<Formula 4>

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

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 limited to their usual or dictionary meanings, and the inventor should appropriately use the concept of terms to explain his or her invention in the best way. It must be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle of definability.

The paint 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 remaining amount of aluminum (Al); and an adhesive resin in which the powder mixture is uniformly dispersed. A paint composition with improved sagging properties, comprising:

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

0.1 to 0.2 parts by weight of a compound represented by the following formula (1),

0.1 to 0.2 parts by weight of a compound represented by the following formula (2) and

It contains 0.1 to 0.2 parts by weight of a compound represented by the following formula (3).

<Formula 1>

<Formula 2>

<Formula 3>

As 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 external environments such as oxygen and moisture that can corrode steel or concrete structures.

0.8% by weight of zinc mixed in aluminum powder contributes to improving 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). The added phosphorus helps the above-mentioned metal powders to be uniformly dispersed in the adhesive resin, and also improves the uniformity and robustness of the aluminum oxide film. It has an improving function.

The above-described powder mixture is mixed with an appropriate adhesive resin and uniformly dispersed to adhere to the surface of the structure, and then sprayed and applied. This adhesive resin can be used by adjusting its viscosity depending on the application method, and it is well known to use polyurethane resin or epoxy resin, which have excellent adhesiveness and elasticity. In particular, polyurethane resin has excellent performance in suppressing penetration of chloride and carbon dioxide gas, and also has good chemical resistance and resistance to penetration of 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 0.1 to 0.2 parts by weight of 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.

The compounds represented by Formula 1 and Formula 2 have a rigid chemical structure, and these compounds undergo a hardening reaction by artificial or solar ultraviolet rays and become solid, so not only does the adhesive strength of the film increase, but also the sagging property of the film. It improves. In addition, the compound represented by Formula 3 further improves the strength of the water retention layer.

In the coating composition of the present invention, the adhesive resin preferably further contains 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 to further enhance the function of the above-mentioned compound.

<Formula 4>

In addition, in the coating composition of the present invention, if the adhesive resin further includes 0.05 to 0.1 parts by weight of a compound represented by the following formula (5) based on 100 parts by weight of the adhesive resin, the above-described effect can be further increased.

<Formula 5>

These compounds represented by Formulas 4 and 5 also have a rigid chemical structure, and these compounds become strong by hardening by artificial ultraviolet light or ultraviolet rays from sunlight, especially on the surface of the water-retaining layer, so the compounds of Formulas 1 and 2 When used in combination with a compound, it further contributes to increasing the adhesive strength of the film and improving film sagging.

In particular, the compound represented by Formula 5 has an H-shaped rigid chemical structure, so the above-described effect can be further increased.

The waterproof and anti-corrosion film adhesion method of the present invention is,

(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 remaining amount of aluminum (Al); and

(b) The prepared powder mixture is mixed with an adhesive resin and 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 Formula 3 based on 100 parts by weight of the adhesive resin. It includes the step of 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 to form a film.

The composite adhesive resin may be further mixed with 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 weight of the compound represented by Chemical Formula 5 based on 100 parts by weight of the adhesive resin. It can include more wealth.

The mixing ratio of the powder mixture and the composite adhesive resin is preferably around 0.2:10 to 3:10. It is very simple to spray the coating solution dispersed and dissolved in an appropriate solvent to form a film by drying and naturally curing at room temperature in the air. and can be constructed economically. After forming the film, the compounds indicated by the chemical formula can be cured using an ultraviolet ray generator, but the curing can be done gradually by the ultraviolet rays contained in sunlight.

The formed film is preferably formed to a thickness of 100㎛ or less based on one application. If necessary, such a film layer is formed by stacking several times, or a film layer formed from the coating composition according to the present invention and a conventional adhesive resin or A stronger film layer can be formed by alternately forming film 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 properties of the film. In addition, it can show excellent protection against penetration of chloride ions, sulfur dioxide gas, moisture, and oxygen, which cause corrosion of steel and concrete structures.

Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described in detail 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 method shown below.

10.08 g (45.4 mmol) of tert-butyl 4-hydroxycinnamic acid (1-c-43a), 100 ml of N,N-dimethylformamide, and 9.4 g of potassium carbonate were added to a 300 ml four-necked flask and stirred for 10 minutes. 10.1 g (53 mmol) of 6-chlorhexyl acrylate was added to this mixture, and the mixture was stirred at 90°C for 6 hours. This reaction mixture was cooled to 10°C, 100 ml of water was added, and stirred for 1 hour. This mixture was filtered to obtain the crude product as a solid. This solid was dissolved in 25 ml of acetone, added dropwise to 45 ml of methanol, and cooled to 0°C. The generated solid was filtered, dissolved again in 12 ml of acetone, added dropwise to 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 added dropwise to this mixture and stirred at 40°C for 5 hours. This reaction mixture was cooled to 30 degrees or lower, and 50 ml of dichloromethane was added. The organic layer was separated and washed four times with 70 ml of water and once with 70 ml of saturated saline solution. The obtained solution was dried with sodium sulfate. After the sodium sulfate was filtered off, the solvent was distilled off. 10 ml of hexane and 4 ml of toluene were added to the obtained solid and stirred at room temperature for 30 minutes. This mixture was filtered and dried to obtain 6.30 g of compound 1-2 (yield 87%).

In a 100 ml three-necked flask, 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 and stirred at 5°C for 10 minutes. Into this mixture, 2.98 g of N,N-diisopropylcarbodiimide was added dropwise while maintaining the temperature at 10 degrees Celsius or lower, and stirred at 30 degrees Celsius for 6 hours. After adding 0.08 ml of water to this 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 to 30 ml of methanol, and cooled to 0°C. By filtering and drying the obtained solid, 4.80 g of compound 1-3 was obtained (yield 69%).

4.8 g of compound 1-3, 1.07 g of 2-hydrazinobenzothiazole, and 20 ml of tetrahydrofuran were added to a 100 ml three-necked flask, and stirred at 50°C for 15 hours. This 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). The solution after passing through the column was filtered and dried to obtain 2.40 g of the compound of Formula 1.

^1H 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 method shown below.

The following compounds were synthesized by the method shown below.

in the reaction vessel , Potassium carbonate, ethanol, and tetrakis(triphenylphosphine)palladium(0) were added and heated and stirred. After performing normal post-processing, purification was performed by column chromatography and recrystallization. Compound 2-1 was obtained.

in the reaction vessel , , N,N-dimethylaminopyridine, and dichloromethane were added. Then, diisopropylcarbodiimide was added and stirred. After performing normal post-processing, purification was performed by column chromatography and recrystallization. Compound 2-2 represented by was obtained.

Compounds 2-1, 2-2, hydrazine monohydrate, and ethanol were added to the reaction vessel and heated and stirred. After performing the usual post-treatment, the product was purified by column chromatography to obtain the compound represented by Formula 2.

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

[Synthesis of compound of formula 3]

The following compounds were synthesized by the method 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, and then stirred for 1 hour. Cyeno[2,3-d]thiazol-2-amine (1 g, 6.4 mmol) was added thereto, heated to 80°C, and stirred to proceed with the reaction. Next, the temperature was lowered to room temperature and 30 ml of water was added to terminate the reaction. 30 ml of 1N NaOH was added to the resulting solid, then 50 ml of chloroform was added again to dissolve it, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and E-K aceate to prepare solid intermediate 3-1 (0.91 g, 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 and stirred for 30 minutes. Sodium nitrite (0.39 g, 5.7 mmol) was dissolved in 16 ml of sulfuric acid, slowly added dropwise, and stirred for 30 minutes while maintaining the temperature below 5°C. N,N-diethylaniline (1.2 g, 8.1 mmol) was dissolved in 5 ml of methanol, slowly added dropwise, and stirred for 2 hours. At this time, the pH was titrated with 2N sodium acetate solution to maintain the pH between 5-7. After completion of the reaction, the mixture was filtered and washed twice with water and methanol to prepare 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-(hexyloxy)phenyl)acetonitrile (0.33 g, 1.7 mmol) were dissolved in 10ml of ethanol. After adding 5 mol% of piperidine to this 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 the water with magnesium sulfate and evaporating the solvent, the compound of Formula 3 (0.45 g, 57%, MS: [M+H]+ = 543.8) was purified through a silica column using chloroform and E?K aceate. was manufactured.

[Synthesis of compound of formula 4]

The following compounds were synthesized by the method shown below.

4-Bromobenzoic acid (50g), tert-butyl alcohol (20.3g), and dimethylaminopyridine (12.2g) were dissolved in dichloromethane, and diisopropylcarbodiimide (DIC, 37.7g) was added dropwise at 35°C. , stirred for 5 hours. The reaction solution 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 extraction was performed with ethyl acetate. The organic layer was washed with 1% hydrochloric acid and saturated saline solution. 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-hydroxybutylacrylate (10.3 g), and 400 ml of DMF were added. DIC (9.0 g) was slowly added dropwise at room temperature and 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 oil-like compound, and the mixture was stirred at room temperature for 9 hours and 45°C for 4 hours. 100 ml of water was added to the reaction system, neutralized with sodium hydroxide, and then extracted 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 solution was filtered, and the organic layer was concentrated. The product was purified by silica gel column chromatography to obtain compound 4-4 (5 g).

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

[Synthesis of compound of formula 5]

The following compounds were synthesized by the method shown below.

In the reaction vessel , triethylamine, dichloromethane, and succinic acid chloride were added and stirred. After performing the usual post-treatment, the product was purified 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 performing the usual post-treatment, the product was purified by column chromatography and recrystallization to obtain compound 5-2.

Compound 5-2 in a reaction vessel, , N,N-dimethylaminopyridine, and dichloromethane were added. Diisopropylcarbodiimide was added and stirred. After performing the usual post-treatment, the product was purified by column chromatography and recrystallization to obtain the compound of formula (5).

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

<Example 1>

A powder mixture consisting of 0.8% by weight of zinc, 0.1% by weight of phosphorus, and the remaining amount of aluminum, an adhesive resin made of polyurethane resin, and a compound represented by Formula 1, Formula 2, and Formula 3 synthesized above based on 100 parts by weight of the adhesive resin. Composite resins containing 0.15 parts by weight and 0.0015 parts by weight of photopolymerization initiator Irgacure907 (manufactured by BASF) were mixed in a ratio of 1:10, dispersed and dissolved in a solvent, and then sprayed on the surface of the concrete to apply at room temperature. After standing for some time, a 35㎛ thick film was formed according to this method, dried and naturally cured at room temperature.

Next, after irradiating ultraviolet rays at an intensity of 40 mW/cm2 for 20 minutes using a high-pressure mercury lamp, 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 Chemical Formula 4 synthesized by the above method was further mixed at a ratio of 0.08 parts by weight based on 100 parts by weight of the adhesive resin.

<Example 3>

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

Comparative Example 1

For the 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 and polyurethane resin were mixed in 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 period of time to form a 35㎛ thick film.

Measurement of adhesive strength of film

The following test was conducted to confirm the adhesion strength of the films formed according to Examples 1-3 and Comparative Example 1.

After forming the aluminum oxide film of Example 1 according to the above-described method on a concrete structure, a 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 adhesion strength of Example 1 was 47kgf/cm ² , the film adhesion strength of Example 2 was 48kgf/cm ² , the film adhesion strength of Example 3 was 50kgf/cm ² , and the film adhesion strength of Comparative Example 1 was 35kgf/cm 2 . It appeared to be about ^cm2 .

Claims (4)

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
In the coating composition for preventing corrosion and improving durability of structures, which consists of an adhesive resin in which the powder mixture is uniformly dispersed,
The adhesive resin is based on 100 parts by weight of adhesive resin.
0.1 to 0.2 parts by weight of a compound represented by the following formula (1),
0.1 to 0.2 parts by weight of a compound represented by the following formula (2) and
Containing 0.1 to 0.2 parts by weight of a compound represented by the following formula (3),
A paint composition with improved sagging properties, wherein the adhesive resin is a polyurethane resin:
<Formula 1>

<Formula 2>

<Formula 3>
In paragraph 1,
The adhesive resin is a paint composition characterized in that it further comprises 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>
(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 remaining amount of aluminum (Al); and
(b) The prepared powder mixture is mixed with an adhesive resin made of polyurethane resin, 0.1 to 0.2 parts by weight of a compound represented by the following formula (1), and 0.1 to 0.2 parts by weight of a compound represented by the formula (2) based on 100 parts by weight of the adhesive resin. And a step of uniformly dispersing 0.1 to 0.2 parts by weight of a compound represented by the following formula (3) in a further mixed composite adhesive resin and spraying it on the surface of the structure to form a film. A waterproof and anti-corrosion film adhesion method comprising:
<Formula 1>

<Formula 2>

<Formula 3>
According to paragraph 3,
The composite adhesive resin is a waterproof and anti-corrosion film adhesion method, characterized in that 0.05 to 0.1 parts by weight of a compound represented by the following formula (4) is further mixed based on 100 parts by weight of the adhesive resin:
<Formula 4>