KR101865092B1 - Anti-corrosion water-soluble paint and varnish composition - Google Patents

Abstract

According to an embodiment of the present invention, there is provided an anticorrosive coating composition comprising aluminum flakes, zinc flakes, water glass, colloidal silica, silane coupling agents, and reaction initiators, wherein the aluminum flakes comprise 1 wt% to 5 wt% Wherein the zinc flake is 5 wt% to 40 wt%, the water glass is 5 wt% to 50 wt%, the colloidal silica is 5 wt% to 50 wt%, the reaction initiator is 1 wt% to 20 wt% The polymer is mixed in an amount of 5% by weight to 50% by weight.

Description

[0001] Anti-corrosion water-soluble paint and varnish composition [

The present invention relates to a naturally drying type anticorrosive coating composition.

In general, the surface of a steel structure has been painted with a rust-preventive coating composition in order to suppress the corrosion of the steel structure. Chromate rust prevention treatment is mainly used. Chromate The anti-rust treatment refers to a method of applying a thin film by supporting a metal in a composition containing chromic acid or dichromate as a main component. The chromate anticorrosive treatment is the most commonly used method of treating the dark, but it contains a hexavalent chromium which is classified as a heavy metal, and thus has a fatal problem that it is harmful to the human body. Hexavalent chromium is known to be a primary carcinogen causing cancer of the larynx and its use is regulated internationally. Countries around the world, including the European Union, regulate the use of chromium in conjunction with lead, cadmium and mercury. Previously, manufacturing and process emissions were regulated, but recently, the final products that were treated with chromate were also regulated. Therefore, development of a rust-preventive coating composition that does not contain hexavalent chromium is required.

However, in order to develop a water-soluble anti-corrosive coating composition containing zinc, it is necessary to cut off the reaction between water and zinc and to enable gelation. There are many difficulties.

On the other hand, the rust-proofing process of a steel structure using a conventional rust-preventive coating composition is problematic in that it requires a heat drying process, which causes a lot of economic loss and adversely affects the environment such as energy consumption and greenhouse gas emission due to the heating and drying process.

Korean Patent No. 10-1247187 (Mar. 19, 2013) Korean Patent No. 10-1559573 (October 5, 2015)

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a waterproof anticorrosion coating composition which does not contain chromium and is excellent in storage stability at room temperature and naturally dried.

According to an embodiment of the present invention, there is provided an anticorrosive coating composition comprising aluminum flakes, zinc flakes, water glass, colloidal silica, silane polymerizates, and reaction initiators, wherein the aluminum flakes comprise 1 wt% to 5 wt% Wherein the zinc flake is 5 wt% to 40 wt%, the water glass is 5 wt% to 50 wt%, the colloidal silica is 5 wt% to 50 wt%, the reaction initiator is 1 wt% to 20 wt% Is mixed with 5% by weight to 50% by weight. The reaction initiator is mixed in an amount of 1% by weight to 50% by weight based on the weight of the silane polymer.

The silane coupling agent is prepared by mixing a silane coupling agent, a reaction initiator, and deionized water, and the silane coupling agent is selected from the group consisting of 3-aminopropyltriethoxysilane (N- (2-aminoethyl) 3-aminopropyltriethoxysilane), vinyltriethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, (3-methacryloxypropyltrimethoxysilane), beta- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, methyl triethoxysilane Is at least one selected from the group consisting of methyltrimethoxysilane, ethyltrimethoxysilane, and N-propyltrimethoxysilane. .

The reaction initiator may be at least one selected from the group consisting of monoethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethyl (N, N-dimethylethanolamine), N, N-ethylethanolamine, N-methyldiethanolamine and N-methylethanolamine. Group, and the like.

The silane coupling agent and the reaction initiator are mixed in a weight ratio of 100: 1 to 30.

The silane polymer is characterized in that the deionized water is mixed with 30 wt% to 70 wt% of the weight of the silane coupling agent and the reaction initiator. More preferably, the silane polymer is characterized in that the deionized water is mixed with 45 wt% to 55 wt% of the weight of the silane coupling agent and the reaction initiator. Wherein the silane polymer is polymerized at 30 ° C to 150 ° C.

Deionized water is mixed in an amount of 5% by weight to 80% by weight of the total weight.

The water glass is at least one selected from the group consisting of lithium silicate, sodium silicate, and potassium silicate, and is mixed with 5 wt% to 50 wt% of the total weight.

The colloidal silica has a particle size of 10 to 90 nm and is mixed with 5 to 50% by weight of the colloidal silica.

The zinc flake is in the form of a plate and has an average thickness of 0.1 mu m to 1.0 mu m and an average width of 5 mu m to 18 mu m.

According to another embodiment of the present invention, there is provided a process for producing a polyurethane foam comprising the steps of: a) mixing and stirring deionized water, a thickener, an anti-settling agent and an antirust agent; b) adding water glass, colloidal silica, silane polymer, Adding an antifoaming agent and a cryoprotectant and stirring the mixture; and c) adding aluminum flake and zinc flake to the result of step b) and agitating the mixture for 4 hours.

According to another embodiment of the present invention, there is provided a rust-preventive coating method of a metal in which a rust-preventive coating composition is applied to the surface of a metal and the rust-preventive coating composition is cured to form a rust-preventive coating.

According to another embodiment of the present invention, there is provided a rust-preventive coating film formed by coating a rust-preventive coating composition on the surface of a metal and naturally drying the applied rust-preventive coating composition.

The rust-preventive coating composition according to an embodiment of the present invention can be naturally dried, including aluminum flake, zinc flake, silane polymer, reaction initiator, water glass, and colloidal silica, It is excellent in storage stability and easy to manufacture and work.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a method for producing a coating composition for rust prevention according to an embodiment of the present invention. Fig.

The present invention relates to a natural drying type anticorrosive coating composition, and more particularly, to a natural drying type anticorrosive coating composition which is excellent in storage stability at room temperature without containing chromium.

According to the present invention, there is provided a natural-drying rust-preventive coating composition characterized by comprising a natural-drying rust-preventive coating composition comprising aluminum flake, zinc flake, water glass, colloidal silica, rust inhibitor and silane polymer.

The naturally drying aqueous inorganic coating composition of the present invention is an eco-friendly anticorrosive paint composition having excellent storage stability at room temperature and excellent rust prevention property, which is produced by using water glass and silane polymer without using harmful heavy metals as conventional environmental pollutants The purpose is to provide.

The naturally drying type rust-preventive coating composition according to an embodiment of the present invention includes aluminum flake, zinc flake, water glass, silane polymer, and reaction initiator.

Aluminum flake and zinc flake are anodic action by self-sacrificing, which acts to prevent corrosion of iron material before it is corroded. Zinc flake and aluminum flake have a higher ionization tendency than iron, so they act as an anode to form a kind of electric circuit, which inhibits iron corrosion. In addition, the silane polymer is adsorbed on the surface of aluminum flakes and zinc flakes before water, thereby blocking the reaction of water with aluminum flakes and zinc flakes to obtain a coating composition having excellent storage stability. The zinc flakes and the aluminum flakes are preferably plate-shaped, and the zinc flakes preferably have an average thickness of 0.1 mu m to 1.0 mu m and an average width of 5 mu m to 18 mu m. Aluminum flakes are preferably used that pass through 100 mesh. The weight ratio of aluminum flake and zinc flake is preferably 1: 5 to 1:15. Mixing of zinc flakes in an amount of 5% by weight to 40% by weight and aluminum flakes in an amount of 1% by weight to 5% by weight makes it possible to prevent tampering and to maintain the best appearance. In the case of a conventional waterproof anti-corrosive coating material containing zinc, zinc dust is used. The rust-preventive paint according to the embodiment of the present invention is advantageous in that the film is coated after applying the paint because there is no gap by using the zinc flake of the plate shape.

Water glass, and colloidal silica serve as binders and serve to fix zinc flakes and aluminum flakes together on the surface of the iron material to which the paint is applied.

The silane polymerizates are formed with zinc flakes and aluminum flakes in multiple layers to protect the surface of the iron material and significantly reduce the rate of corrosion. The silane polymer is prepared by mixing a silane coupling agent, a polymerization initiator, and deionized water. The silane coupling agent may be selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- 3-methacryloxypropyltrimethoxysilane, beta - (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, methyltrimethoxysilane, Silane, ethyltrimethoxysilane, and N0-propyltrimethoxysilane can be used. The reaction initiator may be a monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-methyldiethanolamine, N-methylethanolamine may be used. The deionized water is preferably used in an amount of 30% to 70% by weight of the silane polymer and the reaction initiator. More preferably, the deionized water is used in an amount of 45 to 55% by weight based on the weight of the silane polymer and the reaction initiator. When the deionized water is 30 wt% or less, boiling phenomenon occurs. When the deionized water is 70 wt% or more, the reaction becomes unstable. When the mixing of the silane polymer is unstably completed, the rustproofing property and the storage stability of the finished coating material become poor. There are two methods of mixing the silane polymer according to the embodiment of the present invention. One is to polymerize the selected silane compound and the reaction initiator at a predetermined temperature, and then to add deionized water after cooling, and the other is to introduce a silane compound, a reaction initiator and deionized water together to effect polymerization. A silane polymer can be prepared by any method, but a method of adding a silane coupling agent, a reaction initiator, and deionized water together is more advantageous. This is because addition of deionized water is stable after the silane polymer is stabilized. The silane polymer is preferably added in an amount of 5% by weight to 50% by weight based on the total weight of the coating composition according to the embodiment of the present invention. When it is 5% by weight or less, the storage stability may become poor, and when it is 50% by weight or more, the anticorrosion property may become poor.

The water glass preferably includes at least one selected from the group consisting of Lithium Silicate, Sodium Silicate, Potassium Silicate, and Colloidal Silica. The water glass is preferably added in an amount of 5 to 50% by weight based on the total weight of the coating composition. The water glass enhances the storage stability of the naturally drying type waterborne anti-corrosive coating composition, and also serves as a binder.

The reaction initiator is preferably added in an amount of 1 to 20% by weight based on the total weight of the coating composition. When the addition amount is less than 1% by weight, the effect is insignificant. When the addition amount is more than 20% by weight, problems such as gelation of the rust- have.

0.1 to 1.5% by weight of a dispersing agent, 0.1 to 1.5% by weight of a surfactant, 0.1 to 1.5% by weight of a leveling agent, 0.1 to 2% by weight of a thickener, 0.1% by weight to 2.0% by weight, and 0.1% by weight to 1.5% by weight of an antifoaming agent. Deionized water is used for the remaining weight.

A method of preparing a coating composition for rust prevention according to an embodiment of the present invention will be described with reference to FIG. First, a thickener, an anti-settling agent, an anti-rust agent, and a leveling agent are mixed with deionized water and stirred with RPM 1500 to prepare a paste (S10). A water glass, a silane polymer, a colloidal silica, a wetting agent, a dispersant, a defoaming agent and a cryoprotectant are mixed with the paste thus prepared, followed by stirring for 30 minutes to prepare a paste (S20). Then, zinc flakes and aluminum flakes were placed and stirred at RPM 1200 for 4 hours to complete the anti-corrosive coating composition (S30). The step S30 may be omitted and the aluminum flake and the zinc flake may be mixed together in the step S20 and stirred for 4 hours with the RPM 1200 to complete the rust-preventive coating composition.

According to another embodiment of the present invention, there is provided a rust preventive painting method of a metal for applying a rust-preventive coating composition according to an embodiment of the present invention to a surface of a metal and naturally drying the applied rust-preventive paint composition to form a rust- to provide. The rust-preventive coating composition may be applied to a metal surface using any one of DIP-SPIN, DIP-DRAIN, and SPRAY.

According to another embodiment of the present invention, there is provided a rust-preventive coating film formed by applying a rust-preventive coating composition according to an embodiment of the present invention to a surface of a metal and naturally drying the applied rust-preventive coating composition.

The rust preventive coating preferably has a thickness of 10 탆 to 20 탆, preferably 12 탆 to 15 탆.

Hereinafter, the performance of the anticorrosive coating composition according to the examples of the present invention will be described through performance tests of Examples and Comparative Examples.

Example 1

The mixture was stirred for 30 minutes and then mixed with 30% by weight of water glass, 15% by weight of colloidal silica, 10% by weight of silane polymer, 0.5% by weight of wetting agent 0.5% by weight of deionized water, 0.5% 0.5% by weight of a dispersant, 0.5% by weight of an antifoaming agent and 2.0% by weight of a cryoprotectant were added and stirred for 30 minutes. 2.5% by weight of aluminum flake and 25% by weight of zinc flake were added and stirred for 4 hours to prepare a coating composition.

Example 2

In Example 1, 30 wt% of colloidal silica was added and 15 wt% of water glass was added to prepare a coating composition.

Example 3

In Example 1, 10.9 wt% of deionized water was added, 22 wt% of water glass and 22 wt% of colloidal silica were added to prepare a coating composition.

Example 4

In Example 1, 24.6 wt% of deionized water was added, 30 wt% of water glass was added, and the coating composition was prepared without adding colloidal silica.

Example 5

In Example 1, 14.6 wt% of deionized water was added, 40 wt% of water glass was added, and the coating composition was prepared without adding colloidal silica.

Example 6

In Example 1, 4.9 wt% of deionized water was added, and 50 wt% of water glass was added, and the coating composition was prepared without adding colloidal silica.

Comparative Example 1

In Example 1, a silane polymer was added in an amount of 30% by weight, 17% by weight of water glass was added, and 8% by weight of colloidal silica was added to prepare a coating composition.

Comparative Example 2

In Example 1, 30 parts by weight of a silane polymer was added, 8 parts by weight of water glass was added, and 17 parts by weight of colloidal silica was added to prepare a coating composition.

Comparative Example 3

In Example 1, a silane polymer was added in an amount of 30 wt%, 12 wt% of water glass and colloidal silica was added, and 10.9 wt% of deionized water was added to prepare a coating composition.

Comparative Example 4

Without adding the silane polymer in Example 1, 19.4 wt% of deionized water was added to prepare a coating composition.

Comparative Example 5

In Example 1, 15% by weight of water glass was added, 30% by weight of colloidal silica was added, and 19.4% by weight of deionized water was added to prepare a coating composition without adding the silane polymer.

Comparative Example 6

In Example 1, 22% by weight of water glass and colloidal silica was added without adding a silane polymer, and 20.4% by weight of deionized water was added to prepare a coating composition.

<Test Example>

The coating compositions of Examples 1 to 6 and Comparative Examples 1 to 6 thus prepared were applied to a cold-rolled steel sheet, and dried test pieces were subjected to the following tests.

The test specimens for the test were prepared in the same manner as in Examples 1 to 6 and Comparative Examples 1 to 6 except that the cold-rolled steel sheet was first washed with an organic solvent (xylene) and then washed with an alkali degreasing agent. The coating composition is applied to a thickness of 15 탆 and dried at room temperature (25 캜) for 7 days.

① Adhesion test

In order to test the adhesion of the paint, the surface of the test piece is scratched with a knife according to the test method according to ASTM D 3359, and the cellophane tape is closely adhered so that the untreated part is evenly adhered. Then, the cellophane tape is peeled, Are visually compared and classified into 5B to 0B.

Here, 5B indicates a state in which no peeling is present and 0B indicates a completely peeled state.

② Corrosion resistance (salt water spray exposure test)

In the salt spray exposure test method, the test piece is exposed to a 5% by weight NaCl aqueous solution sprayed at 35 ° C in accordance with KS D 9502 to expose the coating film after 1000 hours.

③ Storage stability test

In the storage stability test method, the coating compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 6 were allowed to stand at room temperature for 180 days, and their viscosity was measured. The viscosity is measured by FORD CUP # No 4 at 20 ° C.

④ Acid and alkali resistance test

The fabricated specimens were immersed in a 5% by weight HCl aqueous solution and a 5% by weight NaCl aqueous solution for 72 hours, respectively, and observed for swelling and exfoliation to determine whether they were excellent, good, normal or defective.

⑤ Water resistance test

The fabricated specimens were immersed in purified water for 1000 hours, and the appearance of bloom, blistering, peeling, etc. were visually observed and classified into four levels of excellent, good, and poor.

<Test Results>

Table 3 shows the storage stability test results of the coating compositions of Examples 1 to 6 and Table 4 shows the storage stability test results of the coating compositions of Comparative Examples 1 to 6. As shown in Table 3, according to Examples 1 to 6 of the present invention, it can be confirmed that the viscosity remains almost the same after 180 days. In Comparative Examples 4, 5 and 6, production was impossible.

Table 5 and Table 6 show the results of KS D 9502 test for rust resistance (corrosion resistance) test.

Table 5 shows the results of the anticorrosion test on the coating compositions of Examples 1 to 6. In some embodiments, it is preferable to appropriately adjust the mixing ratio of water glass and colloidal silica, as in the case of the presence of a blooming phenomenon.

Table 6 shows the results of the anti-corrosive properties of the coating compositions of Comparative Examples 1 to 6. As shown in the table, the comparative examples are incapable of being manufactured (Comparative Examples 4 to 6), and the rustproofing properties are poor (Comparative Examples 1 to 3).

Table 7 shows the adhesion, water resistance, acid resistance and alkali resistance test results for the coating compositions of Examples 1 to 6. As shown in the test results, it is preferable to suitably control the mixing ratio of water glass and colloidal silica in order to satisfy both adhesion, water resistance, acid resistance and alkali resistance.

Table 8 shows the adhesion, water resistance, acid resistance and alkali resistance test results of the coating compositions of Comparative Examples 1 to 6. As shown in Table 8, the comparative example is incapable of being manufactured (Comparative Examples 4 to 6), and is poor in water resistance, acid resistance, alkali resistance and the like (Comparative Examples 1 to 3).

As shown in the above test results, the anti-corrosive coating composition according to the example of the present invention is excellent in storage stability with almost no change for more than 6 months. As in the conventional zinc-containing aqueous anti-corrosive coating material, The problem that occurs is solved. The anti-corrosive coating composition according to the embodiment of the present invention does not require a heating and drying process, enabling natural drying, greatly reducing manufacturing costs by more than 1/3, and solving environmental pollution and greenhouse gas emission problems. The rust-preventive coating composition according to the embodiment of the present invention can provide a rust-preventive property of high corrosion resistance so that even if a metal film to be rust-inhibited is coated with a thin film having a thickness of 12 탆, it passes through a brine spray test for more than 1000 hours. The coating composition according to an embodiment of the present invention can be used as a water-soluble anti-corrosive coating material for preventing rust on metal surfaces by a non-electrolytic thin film coating of silver (metallic silver).

The rust-preventive coating composition according to an embodiment of the present invention provides a highly corrosion-resistant environmentally friendly water-resistant zinc coating material containing no heavy metal (chromium). The coating composition according to an embodiment of the present invention exhibits an excellent effect of preventing electric contact due to contact with dissimilar metals. Also, it has excellent adhesion with top coat and can be used in various kinds of products. The coating film of the anticorrosive coating composition according to the embodiment of the present invention has a tile structure, which is advantageous in shielding effect.

The anti-corrosive coating composition according to an embodiment of the present invention can be applied to a metal surface to be rust-inhibited using a DIP-SPIN, DIP-DRAIN, or SPRAY process. The anti-corrosive coating composition according to an embodiment of the present invention is advantageous in that it is water-soluble and has little VOC so that a pleasant working environment can be obtained. The anti-corrosive coating composition according to an embodiment of the present invention can be provided as a one-pack type room temperature storage type.

The anti-corrosive coating composition according to an embodiment of the present invention can be used for anti-corrosive coating of metal structures such as automobiles, electric / electronic, construction, ships and the like. It can be used for the prevention of piping facilities such as automobile body, automobile interior parts, bridges and structures, vessel interior / exterior materials, street lamps, steel houses, steel pipes, cast iron pipes, steel structures,

Claims (20)

In the anticorrosive paint composition,
A silane coupling agent, a reaction initiator, a silane polymer prepared by mixing deionized water, zinc flakes, aluminum flakes, water glass, colloidal silica,
Wherein the aluminum flake and the zinc flake are in a weight ratio of 1:10 to 1:15,
The silane polymer was mixed in an amount of 10 wt%
Wherein the water glass and the colloidal silica are mixed at a weight ratio of 2: 1. delete The method according to claim 1,
Wherein the reaction initiator is 1% by weight to 50% by weight based on the weight of the silane polymer. The method according to claim 1,
The silane coupling agent may be selected from the group consisting of 3-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3- 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (3-methacryloxypropyltrimethoxysilane), and 3-methacryloxypropyltrimethoxysilane. 3-chloropropyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, N-propyltrimethoxysilane, N-propyltrimethoxysilane, (N-propyltrimethoxysilane). &Lt; / RTI &gt; The method according to claim 1,
The reaction initiator may be at least one selected from the group consisting of monoethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethyl (N, N-dimethylethanolamine), N, N-ethylethanolamine, N-methyldiethanolamine and N-methylethanolamine. Wherein at least one selected from the group is selected from the group consisting of rubbers, The method according to claim 1,
Wherein the silane polymer is mixed with the silane coupling agent and the reaction initiator in a weight ratio of 100: 1 to 100: 30. delete The method according to claim 1,
Wherein the silane polymer is such that the deionized water is mixed with 45 wt% to 55 wt% of the weight of the silane coupling agent and the reaction initiator. The method according to claim 1,
Wherein the silane polymer is polymerized at 30 캜 to 150 캜. The method according to claim 1,
Wherein the deionized water further comprises 5% by weight to 80% by weight of the total weight of the composition. delete The method according to claim 1,
Wherein the water glass is mixed with 30 wt% of the total weight, and the colloidal silica is mixed with 15 wt% of the total weight. delete delete delete delete A rust-preventive coating method for a metal, which comprises applying the rust-preventive coating composition according to claim 1 to a surface of a metal and curing the rust-preventive coating composition to form a rust-preventive coating film. delete A rust-preventive coating film formed by applying the rust-preventive coating composition according to claim 1 to a surface of a metal and naturally drying the applied rust-preventive coating composition. delete

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