KR101892898B1 - Penetrating Ceramic Coating Agents Having Excellent Chemical Resistance and Method for Waterproof and Coating Thereof - Google Patents

Abstract

The present invention relates to a ceramic coating agent to which a zirconium compound and an aluminum compound are added to enhance permeable inorganic nanomaterials and adhesion force during the coating of concrete structure and steel structure, and a permeable waterproof coating method having an excellent chemical resistance in which a nano-sized inorganic material penetrates into voids of the structure by using fluorosilane having a chemical resistance function to form a dense coating film and have enhanced adhesion force. The present invention has an advantage of increasing the durability by increasing the chemical resistance and adhesion force of the structure by sequentially performing lower, middle and upper treatment steps after the surface treatment of the concrete structure and the steel structure.

Description

TECHNICAL FIELD [0001] The present invention relates to a porous ceramic coating material having excellent chemical resistance,

The present invention relates to a water permeable waterproof coating method having excellent chemical resistance, and more particularly, to a water permeable inorganic nano material in waterproof coating of a concrete structure and a steel structure, in which a zirconium compound and an aluminum compound are added The present invention relates to a water permeable waterproof coating method which is capable of penetrating a nano-sized inorganic material into the voids of the structure to thereby enhance the adhesion of the coating film and the chemical resistance by using a ceramic coating agent and a fluorosilane having a chemical resistance function.

Many cracks and leaks such as expansion and contraction of the structure due to increase of external water level, drying shrinkage and temperature change, defects due to insufficient casting and lack of curing management during waterproof painting of concrete structures and steel structures It is difficult to expect a complete method (corrosion protection) of concrete structures and steel structures. In addition, concrete structures and steel structures have a great influence on corrosion of structures due to physical and chemical deterioration factors. Reinforcing the material characteristics of concrete structures and steel structures or ensuring watertightness through thorough construction management is a necessary condition for the structure method But it is not enough for the fundamental method.

On the other hand, most concrete structures and steel structures are exposed to poor physical and chemical environmental conditions from the time of construction, and this environment gradually degrades the performance of concrete structures and steel structures. Since the structure has a characteristic of being corroded by oxygen and moisture in the air, degradation of the material due to corrosion drastically lowers the service life of the structure to be used and negatively affects the safety of the structure, .

Most of the civil engineering structures made of concrete structures and steel structures are exposed to the outside and are affected by the natural environment such as sunlight, snow, and rain. In the case of organic coating materials, due to ultraviolet rays, the coating surface is deteriorated due to the yellowing phenomenon, or the coating film is split due to the brittleness (hardness of the surface), and the structure can not be protected due to peeling, Which leads to an economic loss due to the inconvenience of continual repainting and the additional costs incurred.

As a conventional technique related thereto, Patent Document 0001 discloses a functional ceramic waterproofing / anticorrosion composition excellent in strength, adhesive strength, chemical resistance, heat resistance, ozone resistance, UV resistance and durability, and an environmentally friendly waterproofing / But it is not satisfactory in terms of chemical resistance and adhesion strength since a one-pack type water-soluble composition containing PVC or the like is used.

In addition, the following Patent Document 0002 discloses a " permeable coating method for concrete and cement ", but it does not mention the relationship between the chemical resistance and the adhesion force, as it is a penetration coating method for concrete and cement, .

In the following Patent Document, "Corrosion prevention coating method of offshore wind power steel pipe using metal oxide sol" includes a ceramic corrosion resistant material containing fluorine silane, but the steel pipe for offshore wind power generation is not discolored when exposed to seawater. And the corrosion resistance is strong, so that the maintenance cost of the wind power generator is reduced, but it is not related to chemical resistance and adhesion force.

Therefore, it is necessary to apply waterproof and corrosion resistant materials with excellent chemical resistance in order to increase the durability of the structure.

Korean Patent No. 10-1793194 (Oct. 27, 2017) Korean Patent No. 10-0943158 (2010. 02. 10.) Korean Registered Patent No. 10-1556842 (September 23, 2015)

SUMMARY OF THE INVENTION The present invention has been conceived to solve the above-mentioned problems, and it is an object of the present invention to improve the chemical resistance of the structure by increasing the durability of the concrete structure and the steel structure The purpose of the waterproof coating method is to provide.

The present invention relates to a method of manufacturing a concrete structure, comprising the steps of: (1) forming a base for performing deformation, peeling, removal of foreign matter from a weathered part, and cleaning of a concrete structure and a steel structure; 2) 170 parts by weight of a metal oxide sol of 10 to 20 nm was added to a solution prepared by mixing 150 parts by weight of alkoxysilane and 30 parts by weight of a silane coupling agent on the surface of the structure, 10 to 20 parts by weight of a zirconium compound, 10 to 20 parts by weight of a compound is added and the mixture is allowed to react for 12 hours, thereby applying a low-temperature ceramic coating agent in an amount of 0.10 to 0.30 kg / m 2; 3) After the above-mentioned sub-treatment step, a middle treatment step of applying 0.15 to 0.40 kg / m 2 of a medium ceramic coating agent to which 230 parts by weight of inorganic pigments of various colors and 6 parts by weight of additives are added to 380 parts by weight of the undercoat coating, And a top treatment step of applying 0.10 to 0.45 kg / m < 2 > of an in-phase ceramic coating agent containing 10 to 20 parts by weight of fluorosilane to 616 parts by weight of the above-mentioned intermediate ceramic coating agent after the above-mentioned intermediate treatment step Provides permeable waterproof coating method.

Means for solving the other specific problems according to the present invention are described in the detailed description of the invention.

The ceramic waterproof coating method with excellent chemical resistance according to the present invention uses a ceramic coating agent containing a zirconium compound and an aluminum compound and a chemical resistant fluorosilane in order to enhance permeability inorganic nano material and adhesion performance in coating concrete structures and steel structures The nano-sized inorganic material penetrates into the voids of the structure, and thus the coating film is dense, the adhesion is enhanced, and the chemical resistance is excellent.

In addition, after the surface treatment of the concrete structure and the steel structure is performed, the chemical resistance and the adhesion strength of the structure are improved by sequentially performing the lower, middle, and upper treatment steps, thereby remarkably increasing the durability.

Fig. 1 shows the network structure of a ceramic coating agent containing fluorosilane according to the present invention.
2 shows the network structure of a ceramic coating agent containing fluororesin according to the prior art.
Fig. 3 shows the network structure of a ceramic coating agent containing no fluorine resin according to the prior art.

The water permeable waterproof coating method having excellent chemical resistance will be described in detail below with reference to the accompanying drawings (FIG. 1 to FIG. 3).

The permeable waterproof coating method having excellent chemical resistance according to the present invention comprises: 1) performing a surface cleaning and cleaning operation for removing debris from deformation, peeling, and weathered parts in order to remove foreign substances existing on the surfaces of concrete structures and steel structures A background creating step; 2) 170 parts by weight of a metal oxide sol having a particle diameter of 10 to 20 nm was added to a solution prepared by mixing 150 parts by weight of alkoxysilane and 30 parts by weight of a silane coupling agent, And 10 to 20 parts by weight of an aluminum compound are added to the mixture, and the mixture is allowed to react for 12 hours. The undercoating ceramic coating agent is applied at 0.10 to 0.30 kg / m < 2 > 3) After the sublimation treatment step, the intermediate coating step is applied with 0.15 to 0.40 kg / m 2 of a medium ceramic coating agent to which 230 parts by weight of inorganic pigments and 6 parts by weight of additives are added to 380 parts by weight of the undercoat ceramic coating agent. 4) a top treatment step of applying 0.10 to 0.45 kg / m 2 of a ceramic coating agent for phase-in-phase containing 61 to 6 parts by weight of the intermediate ceramic coating agent and 10 to 20 parts by weight of fluorosilane after the intermediate treatment step.

The permeable waterproof coating method having excellent chemical resistance according to the present invention is a method for coating the surfaces of concrete structures and steel structures with the ceramic coating agent by sequentially performing the base forming step, the under treatment step, the intermediate treatment step and the top treatment step. Hereinafter, the present invention will be described in detail.

1) Steps to create a desktop

   The base forming step is a step of removing foreign substances existing on the surfaces of the concrete structure and the steel structure, and performs a surface cleaning and cleaning work for removing debris such as deformation, peeling and weathered parts of the structure.

2) Substrate treatment stage

   In the priming step, 170 parts by weight of a metal oxide sol of 10 to 20 nm was added to a solution of 150 parts by weight of alkoxysilane and 30 parts by weight of a silane coupling agent, And 10 to 20 parts by weight of an aluminum compound are added and reacted for 12 hours. This is a step of applying 0.10 to 0.30 kg / m 2 of a ceramic coating agent for undercoating.

   A nanometer-sized metal oxide sol is added to a solution prepared by mixing alkoxysilane and a silane coupling agent on the surface of the object to be processed in the base forming step, and then a zirconium compound and / It is preferable that the molecular weight of the reactant produced by charging the aluminum compound does not exceed 3,000. When the molecular weight of the reactant is more than 3,000, the ceramic coating agent for the substrate can not penetrate the substrate, and the coating film is formed thick on the surface, which lowers the adhesion. As the zirconium compound, zirconium acetylacetonate, zirconium acetate, aluminum compounds such as aluminum acetate and aluminum acetylacetonate may be exemplified. It is preferable to use mixed compounds rather than a single compound in order to improve performance.

   10 to 20 parts by weight of the zirconium compound and 10 to 20 parts by weight of the aluminum compound are suitably used, and when the amount is less than 10 parts by weight, the strength of the ceramic coating agent is lowered and the chemical resistance and adhesion performance are lowered. The molecular weight is increased and the adhesion performance is lowered.

   On the other hand, the molecular structure having strong chemical resistance is a network structure in which alkoxysilane, silane coupling agent, nano-sized metal oxide sol, zirconium, aluminum, fluorine and the like are bonded to each other as shown in FIG.

   In particular, the fluorosilane chemically reacts with the surface of the structure to form a coating film having high chemical resistance and durability. In addition, fluorine silane has the smallest intermolecular attraction among all the compounds, and since the surface tension is small, it is difficult to wet the solvent, so the resistance to the chemical is strengthened and the chemical resistance can be improved.

  Wherein the alkoxysilane is selected from methyltriethoxysilane (MTES), tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), diphenyldiethoxysilane (DPDES), diphenyldimethoxysilane It may be more than one kind. The aminosilane, which is the silane coupling agent, is preferably selected from the group consisting of N- (? -Aminoethyl) -? - aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane and bis -? - trimethoxysilylpropylamine It may be more than one kind.

   When the alkoxysilane is mixed with the silane coupling agent, the weight ratio of the alkoxysilane to the silane coupling agent is preferably 5: 1. When the ratio of the alkoxysilane to the silane coupling agent exceeds 5: 1, If the ratio is less than 5: 1, not only the adhesion to various substrates is reduced but also the penetration resistance to sodium ions is lowered.

   It is also preferable to apply a ceramic coating agent for a low temperature of 0.10 to 0.30 kg / m 2. If the coating amount is less than 0.10 kg / m 2, sufficient adhesion is not achieved between the undercoat ceramic coating agent and the surface of the structure, resulting in deterioration of the adhesion. When the coating amount is over 0.30 kg / m 2, the surface roughness is weak.

- Manufacture of Ceramic Coatings for Undercoats

 150 parts by weight of methyltrimethoxysilane and 30 parts by weight of? -Aminopropyltriethoxysilane were mixed in a reactor for producing a ceramic coating agent. Then, 60 parts by weight of silica sol having a particle size of 10 to 20 nm, 60 parts by weight of titania sol, Were gradually added dropwise. 10 parts by weight of zirconium acetylacetonate, 5 parts by weight of zirconium acetate, 10 parts by weight of aluminum acetate and 5 parts by weight of aluminum acetylacetonate are continuously added for 12 hours to obtain a low-temperature ceramic coating agent.

3)

The intermediate treatment step is a step of applying a moderate ceramic coating agent to which 380 parts by weight of the undercoat ceramic coating agent is added with 230 parts by weight of an inorganic pigment and 6 parts by weight of an additive. Specifically, 180 parts by weight of titanium dioxide (TiO ₂ ), 50 parts by weight of cyan blue, and a dispersant, a defoaming agent and a leveling agent were added as an additive, respectively, to prepare an intermediate ceramic coating agent. / M < 2 >. If the coating amount is less than 0.15 kg / m 2, it is difficult to conceal the surface, and the interlayer adhesion is decreased. When the coating amount is more than 0.40 kg / m 2, the coating film flows down and wrinkles occur.

 - Preparation of medium-sized ceramic coating agent

  In the ceramic coating material for intermediate use, 180 parts by weight of titanium dioxide, which is an inorganic pigment, 50 parts by weight of cyan blue, 2.5 parts by weight of BYK-110 as a dispersant, 2.0 parts by weight of BYK-066N as a defoaming agent, BYK And 1.5 parts by weight of -333, respectively.

4) Phase treatment process

   The upper phase treatment step is a step of applying 0.10 to 0.45 kg / m < 2 > of an upper ceramic coating agent containing 61 to 6 parts by weight of the above-mentioned medium-range ceramic coating agent and 10 to 20 parts by weight of fluorosilane. Heptadecafluoro-1,1,2,2-tetradecyltrimethoxysilane and Tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane are added as the fluorine silane and aged at 80 ° C for 24 hours to prepare a ceramic coating for topical use.

   If the amount of the fluorosilane added is less than 10 parts by weight, the chemical resistance is deteriorated. If the amount of the fluorosilane is more than 20 parts by weight, the fluorosilane is not mixed with the ceramic coating agent. If the application amount of the above-mentioned ceramic coating agent for phase-in is less than 0.10 kg / m 2, it is difficult to conceal the intermediate surface and the interlayer adhesion force is also lowered, and when the coating is applied above 0.45 kg / m 2, the coating film flows down and wrinkles occur.

- Preparation of Ceramic Coating Agent for Phase Coating

 5 parts by weight of heptadecafluoro-1,1,2,2-tetradecyltrimethoxysilane and 5 to 10 parts by weight of tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane were added to 616 parts by weight of the above-mentioned ceramic coating agent for medium- And aged at 80 ° C for 24 hours to prepare a ceramic coating for topical use.

   On the other hand, in the case of the water-treated concrete structure, the roughness of the surface is not smooth than the general concrete structure or the steel structure. Therefore, after the above-mentioned ground treatment step, the background adjustment step is added and then the water-

   The base adjusting step may include adjusting the base adjusting material prepared by mixing 342 parts by weight of cement, 342 parts by weight of silica sand No. 8 and 76 parts by weight of fly ash to 380 parts by weight of the undercoat ceramic coating agent after the undercoating treatment step is performed at 0.50 to 2.30 kg / . In addition, it is preferable to coat the ceramic-based desk adjusting material with a thickness of 0.50 to 2.30 kg / m 2 after the above-mentioned sub-treatment step. When the coating amount is less than 0.50 kg / m 2, bubbles are generated through the pores, and bubbles are continuously generated in the subsequent process. When the coating amount is 2.30 kg / m 2 or more, the coating is too thick.

- Manufacture of backing materials

 343 parts by weight of cement, 342 parts by weight of silicate No. 8 (not less than 80 mesh and not more than 0.2 mm) and 76 parts by weight of fly ash were added to 380 parts by weight of a ceramic coating material for undercoating, and sufficiently stirred so as not to be aggregated with each other.

 Hereinafter, the present invention will be described in greater detail with reference to the following examples. It is to be understood that the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention .

1) After the surface preparation and cleaning to remove the foreign material on the surface of the concrete object in the base making step, the ceramic coating material for undercoat prepared above was applied to be 0.14 kg / m 2 by using a brush and roller in the lower treatment step Respectively.

2) Then, the above-prepared medium ceramic coating agent was coated at 0.25 kg / m 2 using a brush, roller, and spray.

3) Finally, the above-prepared ceramic coating agent (5 g of Heptadecafluoro-1,1,2,2-tetradecyltrimethoxysilane and 5 g of tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane as a fluorine silane) To 0.25 kg / m 2.

10 g of heptadecafluoro-1,1,2,2-tetradecyltrimethoxysilane and 1 g of Tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane were added as fluorosilanes in the ceramic coating for phase inks, respectively, in comparison with Example 1 And the remaining processes were the same.

Compared with the above-mentioned Example 2, the remaining process was the same except that the material to be treated was steel instead of concrete.

As compared with Example 1, 4 g of heptadecafluoro-1,1,2,2-tetradecyltrimethoxysilane and 1 g of Tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane were added as fluorosilanes, And the remaining processes were the same.

In place of 10 g of zirconium acetylacetonate, 5 g of zirconium acetate, 10 g of aluminum acetate and 5 g of aluminum acetylacetonate, 25 g of zirconium acetylacetonate and 25 g of aluminum acetate were added in the preparation of the ceramic coating agent for lowering, The remaining steps were the same except that the injection point was the same.

Compared with the above-mentioned Example 1, the remaining steps were the same except that 0.09 kg / m < 2 > was applied instead of 0.14 kg / m < 2 >

Compared with the above-mentioned Example 1, the remaining steps were the same except that 0.45 kg / m < 2 > was applied instead of 0.25 kg / m < 2 >

Compared with the above-mentioned Example 1, the other steps were the same except that 0.09 kg / m < 2 > was applied instead of 0.25 kg / m < 2 >

[Comparative Example 1]

1) In comparison with Example 1, 280 g of methyltriethoxysilane and 40 g of 3-aminopropyltriethoxysilane were mixed in a 5 L reactor equipped with a cooler and a stirrer, followed by the addition of 160 g of isopropanol, 50 g of silica sol (30 wt% SiO ₂ ) having an average particle size of 12 nm, 60 g of a titanium sol having an average particle size of 10 nm, and 40 g of alumina sol were gradually added dropwise under heating and stirring for a period of time. , The pH was adjusted to 4, the reaction was continued for 24 hours, and the reaction was carried out for 5 days to obtain a ceramic coating agent for lowering (same as in Example 1 of Patent Document 3).

2) A ceramic coating material for intermediate use was prepared by adding inorganic pigments of various colors to the above ceramic coating material for undercoating.

3) 12 g of heptadecafluorodecyltrimethoxysilane as fluorosilane was added to the above ceramic coating agent for use as a top coat ceramic coating agent, 10 g of trimethylamine was added as a curing catalyst, and the mixture was aged at room temperature for 5 days to prepare a ceramic coating agent for topical use (The same as in Example 1 of the above-mentioned Patent Document 3) was used, and the other was coated in the same manner as in Example 1.

[Comparative Example 2]

The fluorinated silane was prepared and coated in the same manner as in Example 1, except that the fluorine silane was removed in the top treatment step as compared with the above-mentioned Example 1.

[Comparative Example 3]

Compared with the above Example 1, a ceramic coating agent for undercoating was prepared and coated in the same manner as in Example 1 except that zirconium acetylacetonate, zirconium acetate, aluminum acetate, and aluminum acetylacetonate were not added.

Hereinafter, the performance tests on the test pieces prepared in Examples 1 to 8 and Comparative Examples 1 to 3 were carried out as follows.

<Test Example>

The performance comparison experiment was carried out as shown in Table 1 according to the standard specification of the Ministry of Environment Waterworks Construction (2014) 4.3.6 Quality test of ceramic metal waterproofing and method and KS F 4929 ceramic metal-containing resin waterproofing and abrasive standard.

<Experimental Results>

Performance comparison chart Test Items unit Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 One 5% HCl MPa 3.00 3.01 4.25 2.56 2.68 2.60 2.67 2.59 2.22 1.50 2.10 2 1% NaClO MPa 3.05 3.10 4.20 2.59 2.67 2.90 2.67 2.60 2.26 1.60 2.20 3 5%
NaOH MPa 3.05 3.18 4.22 2.64 2.69 2.97 2.73 2.65 2.21 1.60 2.20 4 freezing
Fusion MPa 3.01 3.02 - 2.61 2.69 2.71 2.65 2.62 2.17 1.50 2.15 5 Weatherability MPa 3.01 3.03 - 2.59 2.60 2.64 2.61 2.61 2.20 1.45 2.13 6 Wet
dry MPa 3.10 3.15 4.25 2.71 2.91 2.90 2.71 2.74 2.29 1.60 2.25 7 Underwater
Immersion MPa 3.10 3.15 4.28 2.53 2.65 2.95 2.66 2.57 2.38 1.65 2.26 8 Room temperature MPa 3.12 3.20 4.30 2.71 2.80 2.73 2.67 2.72 2.89 3.01 2.30 9 Absorbency kg / m &lt; 2 &gt; h ^0.5 0 0 - 0 0 0 0 0 0 0.05 0.05 10 Chlorine ion penetration
Resistance Coulomb 0 0 - 0 0 0 0 0 0 109 113 11 Appearance - no problem no problem no problem no problem no problem no problem no problem no problem no problem no problem no problem 12 Bending resistance - 〃 〃 〃 〃 〃 〃 〃 〃 〃 Exfoliation Exfoliation 13 Impact resistance - 〃 〃 〃 〃 〃 〃 〃 〃 〃 Exfoliation Exfoliation 14 Permeability - 〃 〃 〃 〃 〃 〃 〃 〃 〃 Pitcher Pitcher 15 Chloride ion penetration resistance Mm 0 0 0 0 0 0 0 0 0 2.4 2.85 16 Moisture resistance - no problem no problem no problem no problem no problem no problem no problem no problem no problem Boo Exfoliation 17 Low temperature ·
High temperature
Repeat resistance - 〃 〃 〃 〃 〃 〃 〃 〃 〃 crack Exfoliation

<Analysis of Test Results>

The results of various tests for Examples 1 to 8 and Comparative Examples 1 to 3 show that the application amount of the ceramic coating agent and the fluorosilane amount according to the permeable waterproof coating method having excellent chemical resistance of the present invention Examples 1, 2 and 3, which are the most preferable examples within the defined range, have excellent performance in terms of chemical resistance and adhesion strength of all items as compared with the comparative examples 1 to 3, And it was found. Particularly, Examples 1, 2 and 3 show that when the fluorosilane addition, the zirconium and aluminum compounds of Comparative Example 1 are not added, the zirconium and aluminum compounds of Comparative Example 3 are added when fluorosilane of Comparative Example 2 is not added It is understood that the chemical resistance and the adhesion performance are superior to those in the case of not using the resin.

The reason is that the adhesion strength was lowered when zirconium and aluminum compounds were not added. Furthermore, as can be seen from [Figure 1] to [Figure 3], when fluorine silane of [Figure 1] is used, fluorine is easily exposed to the surface of the coating film and chemical resistance is excellent. On the other hand, , Only a part of fluorine was exposed on the surface of the coating film, and the ceramic coating agent containing no fluorine in [Fig. 3] was found to have deteriorated chemical resistance.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes and modifications may be made without departing from the scope of the invention. . Accordingly, it should be apparent that the true scope of the present invention is defined by the following claims.

Claims (7)

1) a step of making a base to clean and clean the debris on the surface of the concrete structure and the steel structure;
2) 170 parts by weight of a metal oxide sol of 10 to 20 nm was added to a mixture of 150 parts by weight of alkoxysilane and 30 parts by weight of a silane coupling agent on the surface of the object to be processed in the above base forming step, and then 10 to 20 parts by weight of a zirconium compound 10 to 20 parts by weight of an aluminum compound is added to the mixture, and the mixture is allowed to react for 12 hours, thereby applying a low-temperature ceramic coating agent in an amount of 0.10 to 0.30 kg / m 2;
3) After the sublimation treatment step, a middle treatment step of applying 0.15 to 0.40 kg / m 2 of a medium ceramic coating agent to which 230 parts by weight of inorganic pigments and 6 parts by weight of additives are added to 380 parts by weight of the undercoat ceramic coating agent;
4) a top treatment step of applying 0.10 to 0.45 kg / m 2 of an in-phase ceramic coating agent containing 61 to 6 parts by weight of the intermediate ceramic coating agent and 10 to 20 parts by weight of fluorosilane after the intermediate treatment step, Excellent permeability waterproof coating method.
The method according to claim 1,
The alkoxysilane may be selected from the group consisting of methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), diphenyldiethoxysilane (DPDES) , And diphenyldimethoxysilane (DPDMS). &Lt; / RTI &gt;
3. The method of claim 2,
The silane coupling agent during the undercoating step is selected from the group consisting of 1 (1) selected from N- (? -Aminoethyl) -? - aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane and bis Or more, which is excellent in chemical resistance.
The method of claim 3,
Wherein the metal oxide sol is at least one selected from the group consisting of silica sol, alumina sol, and titania sol in the undercoating step.
5. The method of claim 4,
Wherein the zirconium compound is zirconium acetylacetonate or zirconium acetate during the undercoating step, wherein the zirconium compound is zirconium acetylacetonate or zirconium acetate.
6. The method of claim 5,
Wherein the aluminum compound in the undercoating step is aluminum acetylacetonate or aluminum acetate, and has excellent chemical resistance.
The method according to claim 6,
Wherein the fluorine silane in the top treatment step is heptadecafluorotetradecyl trimethoxysilane, tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane, and has excellent chemical resistance. Painting method.

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