KR102127831B1 - Paste for underwater coating having surfactant and silane coupling agent - Google Patents

Abstract

Proposed is a paint for underwater painting, comprising a surfactant and a silane coupling agent. The paint for underwater painting can improve anti-rust and anti-corrosion performance, prevent safety accidents caused by corrosion in marine structures, facilitate repair works on the marine structures, and enable the repair works with a simple process and at low costs. The paint is formed as a mixture of a base component (a) and a hardening component (b), wherein the base component (a) includes an underwater hardening-type modified epoxy resin, ceramic powder, an anionic surfactant, and a silane coupling agent, and the hardening component (b) includes an underwater hardening-type aliphatic amine resin and ceramic powder. Moreover, in the base component (a), the modified epoxy resin comprises 50-100 parts by weight of sheet-shaped glass flakes.

Description

Paint for underwater coating containing surfactant and silane coupling agent {Paste for underwater coating having surfactant and silane coupling agent}

The present invention relates to a paint for underwater painting, and more particularly, to a paint that restores a corroded marine structure by painting in water by using a surfactant and a silane coupling agent.

The coastal area has a number of ports and docks, offshore structures such as chemical plant complexes, ironworks and power plants. Recently, marine wind power generation facilities, which are eco-friendly energy, have been spotlighted as alternative energy for the future. On the other hand, for rust prevention and protection of these marine structures, a huge amount of repairs are made every year. If the marine structures are corroded and fail to function, they can cause serious safety accidents. However, due to the nature of the offshore structure, it is almost impossible to repair the structure without disturbing seawater, and various construction methods have been proposed. However, these methods have poor economic efficiency due to maintenance periods and maintenance costs.

Paints for repairing offshore structures are proposed in Korean Patent Nos. 10-0594508, 10-0630439, 10-0717174, and 10-1513530. However, the conventional paint is applied in a place where there is no contact with water, which is a non-underwater place when repairing. Specifically, it consists of a process of dismantling and repairing offshore structures that require repair, and mounting the repaired offshore structures back to their original locations. If this is done, a lot of maintenance time and maintenance cost are required. Accordingly, there is a need for a method that improves anti-corrosion and anti-corrosion performance, enables painting in water, and facilitates the maintenance and repair of offshore structures.

The problem to be solved by the present invention is to improve the anti-rust and anti-corrosion performance, prevent safety accidents due to corrosion of offshore structures, smoothly repair offshore structures, and implement a simple process and repair at a low cost. It is to provide a paint for water coating containing an active agent and a silane coupling agent.

In order to solve the problems of the present invention, the paint for water coating containing a surfactant and a silane coupling agent is made of a mixture of a main component (a) and a curing component (b), and the main component (a) is a water-curable modified epoxy Resin, ceramic powder, anionic surfactant, and silane coupling agent are included, and the curing component (b) includes water-curable aliphatic amine resin and ceramic powder, and the main component (a) comprises plate-like glass flakes on the modified epoxy resin 50 ~100 parts by weight.

In the coating of the present invention, the water-curable modified epoxy resin may be an water-curable modified epoxy resin having an equivalent weight of 190 g to 210 g/eq. The water-curable modified epoxy resin is a bisphenol A-type epoxy resin, and may be at least any one selected from a Novolac epoxy and a cycloaliphatic epoxy. The water-curable modified epoxy resin is added with at least one selected from bisphenol diglycidyl ether polymer, ethylene glycol monoethyl ether, glycyoxypropyl trimethysilane, and dicyclopentadiene polymer to lower the intramolecular polar group and reduce the molar volume. Can be increased. An acid-modified polyolefin may be mixed with the water-curable modified epoxy resin. The ceramic powder may include at least one selected from silicon carbide, alumina, titanium dioxide, calcium carbonate, mica, silica, barium sulfate, or rust preventive pigments.

In the preferred coating material of the present invention, the surfactant pushes the moisture off the surface of the marine structure, and sulfate, sulfonate, and phosphate-based ammonia lauryl sulfate, sodium lauryl sulfate, and sodium It may be at least any one selected from laureth sulfate, dioctylsodium sulfosuccinate, carboxylate, sodium stearate, sulfonate, sulfate ester salt, and phosphate ester salt. The silane coupling agent may hydrolyze moisture remaining in the coating material, and may be at least one selected from epoxy-based silane, amino-based silane, methacryoxy-based silane, chloropropyl-based silane, and mercapto-based silane.

In the paint of the present invention, the cured component (b) of the paint may include a water-curable aliphatic amine resin that undergoes a curing reaction in water. In addition, the coating may include fiber-reinforced fibers. The paint may be applied to at least one selected from compression and elastic fabrics covering glass structures, glass tapes, glass cloths, and meshes.

According to the paint for underwater coating containing the surfactant and the silane coupling agent of the present invention, by including the surfactant and the silane coupling agent, rust prevention and anti-corrosion performance is improved, to prevent safety accidents due to corrosion of marine structures, marine The structure can be repaired smoothly and can be repaired with a simple process and low cost.

1 is a schematic diagram showing the principle of coating the paint for underwater coating according to the present invention.
2 is a schematic view for explaining the hydrolysis mechanism of the silane coupling agent according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments described below may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. The embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art. On the other hand, in the drawings, the thickness of the films (layers, patterns) and regions may be exaggerated for clarity. Also, when a film (layer, pattern) is said to be on top, top, bottom, or one side of another film (layer, pattern), it may be formed directly on another film (layer, pattern) or may be different between them. A film (layer, pattern) may be interposed.

The embodiment of the present invention includes a surfactant and a silane coupling agent, thereby improving rust prevention and anticorrosive performance, preventing safety accidents due to corrosion of offshore structures, and smoothly repairing offshore structures, with simple processes and fewer Present a paint for underwater painting that can be repaired at a cost. To this end, the coating material containing the surfactant and the silane coupling agent will be specifically described, and the properties of the coating material will be described in detail. The paint according to the embodiment of the present invention is applied to all marine structures installed in the sea, such as a pier docking facility, ship, offshore plant, offshore jacket, offshore wind power generation facility, and the like. In the following, it will be described by dividing it into a coating layer and a coating method using a paint for underwater painting.

<Coating layer with paint for underwater painting>

1 is a schematic diagram conceptually showing a principle in which a paint for underwater painting according to an embodiment of the present invention is coated. However, the drawings are not expressed in a strict sense, and for convenience of description, there may be components not shown in the drawings.

According to FIG. 1, the paint for underwater painting of the present invention is coated on the surface of a marine structure (PL) to form a coating layer (10). The main component (a) and the curing component (b) are mixed in the coating material of the coating layer 10, and contain a surfactant 20 and a silane coupling agent. The surfactant 20 improves the adhesion of the coating layer 10 by pushing moisture on the surface of the offshore structure PL by the principle of pushing moisture (H ₂ O). In addition, the silane coupling agent increases the adhesion of the coating layer 10 by hydrolyzing moisture remaining inside the coating layer 10 coated in water. The thickness of the coating layer 10 has a degree of maintaining mechanical properties that are not damaged by external impact and properties that prevent corrosion by salt of seawater for a long time. To this end, the thickness of the coating layer 10 is preferably 500 ~ 1,000㎛.

The coating layer 10 is formed by mixing the main component (a) and the curing component (b). At this time, the main component (a) and the curing component (b) may be mixed in a ratio of 5:1. The main component (a) contains 80 to 90 parts by weight of plate-like glass flakes and 15 to 30 ceramic powders based on 100 parts by weight of the water-curable resin. Parts by weight and other additives. The water-curable resin is preferably a modified epoxy resin having an equivalent of 190g to 210g/eq. At this time, the modified epoxy resin having an equivalent weight of 190 g to 210 g/eq is mixed with a plate-shaped glass flake, a ceramic powder part, and an additive with an ideal viscosity and reactivity to be mixed with an aliphatically modified amine resin for water curing at an ideal mixing ratio of 5:1 to improve the bonding strength. Improve it further. The equivalent of 190 g to 210 g/eq is based on the technical idea of water coating by underwater curing of the present invention, and is not obtained by repeated experiments.

The modified epoxy resin is preferably a bisphenol A-type epoxy, and may be used by mixing any one or two or more selected from a novolac epoxy and a cycloaliphatic epoxy, if necessary. The bisphenol A-modified epoxy resin is excellent in mechanical properties, electrical properties, dimensional stability and chemical resistance. In addition, to the water-curable resin, a bisphenol diglycidyl ether polymer, ethylene glycol monoethyl ether, glycyoxypropyl trimethysilane, and dicyclopentadiene polymer are added to decrease the polar group in the molecule and molar. It is good to increase the volume. As described above, when the polar group in the molecule is lowered and the molar volume is increased, the insulation resistance and stiffness of the water-curable modified resin can be increased. In this case, it is possible to block current due to a short circuit that may occur in the offshore structure PL.

The acid-modified polyolefin may be mixed with the water-curable resin according to the embodiment of the present invention. The acid-modified polyolefin is a polyolefin grafted with an acid such as maleic anhydride or carboxylic acid. At this time, examples of the polyolefin include polyethylene and polypropylene. Since the acid-modified polyolefin has excellent adhesion to metal and sealing properties, it improves the adhesion of the paint.

The plate-like glass flakes prevent diffusion and permeation of moisture, halogen group ions, acid and alkali ions, and the like. In particular, since the flake prevents the diffusion and permeation of the moisture, the water-coating properties are further improved. In addition, the flakes improve the coating film strength and abrasion resistance of the coating layer 10 to reduce hardening shrinkage to prevent cracking.

The plate-like glass flakes include a glass network former and a network modifier. SiO ₂ is preferably used as the glass network forming agent, and various properties of the flake are adjusted as the network modification agent. The network modifier may be at least one selected from the group consisting of Al ₂ O ₃ , B ₂ O ₃ , MgO, CaO, SrO, ZnO, Na ₂ O, Li ₂ O, K ₂ O, and mixtures thereof. The plate-shaped glass flake may contain 80 to 90 parts by weight with respect to the water-curable resin. The plate-shaped glass flakes are 80 If it is smaller than parts by weight, corrosion resistance to seawater is deteriorated, and if it exceeds 90 parts by weight, it is difficult to manufacture exceeding the volume concentration of the coating layer 10, and coating property including adhesion is rapidly reduced. At this time, the plate-shaped glass flakes have an average length of 15 to 55 µm, and an average thickness of 0.1 to 0.5 µm.

The ceramic powder may be at least one selected from silicon carbide, alumina, titanium dioxide, calcium carbonate, mica, silica, barium sulfate, and rust preventive pigments having an average particle size distribution of 0.2 to 50 μm. The ceramic powder may be mixed in an amount of 15 to 30 parts by weight with respect to the water-curable resin. The ceramic powder serves to improve durability, improve mechanical strength, improve workability and adjust gloss. If the ceramic powder is less than 15 parts by weight, the mechanical strength may deteriorate, and if it exceeds 30 parts by weight, it is difficult to manufacture exceeding the volume concentration of the coating layer 10, and coating property including adhesion is rapidly reduced.

Other additives include anti-settling agents that prevent the sedimentation of mixtures of anti-adhesion paints, anti-foaming agents that improve the smoothness of the surface by preventing air bubbles from forming on the surface of the coating film, and dispersants that uniformly disperse the mixture. , It is preferable that the additive contains 1 to 5 parts by weight based on 100 parts by weight of the coating layer 10. More preferably, 0.8 to 4 parts by weight of the anti-settling agent mixed 1:1 by weight ratio of amide wax and benton, 0.1 to 0.5 parts by weight of the silicone antifoaming agent, and 0.1 to 0.5 parts by weight of the dispersant may be mixed. In addition, the dispersant is not particularly limited and may be selected and used among conventional dispersants according to the manufacturer's needs. Examples of the dispersant include BYK-181, BYK-183, BYK-184, BYK-190, BYK-192, etc. Can be lifted. Thickeners and the like may be added to the additives in addition to those previously presented.

Meanwhile, the additive includes a surfactant having a property of repelling moisture present on the surface of the marine structure (MS) to which the coating layer 10 is attached. If the content of the surfactant is too small, the adhesion strength in the water of the coating layer 10 decreases, and if the content of the surfactant is too large, the viscosity of the coating layer 10 increases and a large amount of bubbles are generated. The content of the surfactant may vary depending on the composition, thickness, etc. of the coating layer 10 of the present invention. The surfactant is preferably an anionic surfactant. The anionic surfactants include sulfate, sulfonate, and phosphate-based ammonium lauryl sulfate, sodium lauryl sulfate, sodium laureth sulfate, dioctylshodium sulfosuccinate, carboxylate, and sodium stearate It may be any one or two or more selected from rate, sulfonate, sulfate ester salt, and phosphoric acid ester salt.

The additive may include a silane coupling agent. The silane coupling agent improves the adhesion of the coating layer 10 to the surface of the marine structure (PL) and improves mechanical properties such as salt water resistance. In addition, the silane coupling agent increases the adhesion of the coating layer 10 by hydrolyzing moisture remaining inside the coating layer 10. The silane coupling agent is an epoxy-based silane (eg, γ-glycidoxypropylmethyldiepoxy silane, γ-glycidoxypropyltrimethoxy silane, γ-glycidoxypropyltriethoxy silane), amino silane (eg , γ-aminopropyltrimethoxy silane, γ-aminopropyltriethoxy silane, γ-aminopropyltrialkoxy silane), metacrioxy silane (γ-methacryloxypropyltriethoxy silane, γ-methacryloxy Propyl trimethoxy silane), chloropropyl-based silane (γ-chloropropyl triethoxy silane), mercapto-based silane (γ-mercaptopropyl trimethoxy silane), or the like, or one or more selected from the group consisting of Can be used in combination.

The surfactant and the silane coupling agent according to the embodiment of the present invention are based on the technical idea of improving the properties of water coating. In the case of the surfactant, stabilization is achieved by changing the properties between the two materials by changing the interfacial tension. In addition, the surfactant pushes the moisture present between the coating layer 10 and the surface of the offshore structure (PL). The surfactant is preferably an anionic surfactant. The anionic surfactant is active when the hydrophilic part dissociates in water to become an anion so that the interface of the hydrophilic part in contact with moisture becomes an anion. Anionic surfactants are excellent in cleaning and foaming, so they are excellent in removing oil. As described above, the anionic surfactant can exhibit the above properties because it has a structure that easily escapes after penetrating into the material.

In the case of the silane coupling agent, it serves as a cross-linking role between the organic component and the inorganic component contained in the main component (a) and the curing component (b) included in the coating layer 10, thereby increasing adhesion. The silane coupling agent is also helpful for dispersion stability because it acts as a bridge between organic and inorganic substances. As shown in FIG. 2, the silane coupling agent causes hydrolysis of the moisture remaining in the coating layer 10 and combines with the ceram film powder (CP) to remove residual moisture.

The curing component (b) contains 80 to 90 parts by weight of the curing agent, ceramic powder and other additives relative to the entire curing component (b). The curing agent is added for the curing performance of the paint in water. When the content of the curing agent is less than 80 parts by weight, the curing speed of the coating material applied to the structure is slow, resulting in poor workability, and the content of the curing agent is 90 parts by weight. When exceeded, the stability of the coating applied to the structure is deteriorated. The curing agent is not particularly limited, but preferably, a modified aliphatic amine having an active hydrogen equivalent of 60 to 70 is most preferred. The modified aliphatic amine resin forms an active hydrogen equivalent of 60 to 70, and the amine causes water curing in the Mannich reaction. Other additives may further include a curing accelerator and a water absorbent in addition to the antifoaming agent, dispersing agent, and plasticizer described above.

In an embodiment of the present invention, fiber-reinforced fibers may be added to improve the mechanical properties of the paint. The fiber may be at least one of ceramic fiber such as glass fiber, plastic fiber such as engineering, and metal fiber such as titanium. The paint may be applied to at least one selected from compression and resilient fabrics, glass tape and glass cloth, and mesh covering or surrounding the marine structure PL. For example, after wrapping the marine structure (PL) with a compressive and elastic fabric, a glass tape and a glass cloth, a mesh, etc., the paint of the present invention can be applied thereon. .

<Coating method of paint for underwater painting>

The coating method according to the embodiment of the present invention will be described. The surface of the offshore structure PL can be cleaned prior to coating. The method of cleaning the surface of the offshore structure PL is not particularly limited, and foreign matter can be removed by an appropriate method if necessary. Among them, short blast or power tools can be used. Hereinafter, to describe the properties of the paint of the present invention in detail, the following examples are presented. However, the present invention is not particularly limited to the following examples. In addition, the physical properties shown in Examples and Comparative Examples show values measured by the following method. At this time, the paint for water coating was coated on a test piece of 300×100×3.2 (width×length×thickness) and cured in water for 24 hours, and then measured by a curing test method of the KS M 5000 coating film.

-The adhesion was evaluated according to the method of ASTM D 4541 after curing the test piece coated in water for 24 hours in water.

-The impact test was carried out immediately after taking out the test piece cured in water by KS D 8502 for 24 hours in water and quickly removing the moisture attached with a soft and clean cotton cloth. A steel ball of 650 g was dropped on the test piece vertically on the coating film at a height of 2,400 mm. After the direct impact, all the coating films that were likely to fall off were removed, and the area of the exposed portion was measured, and the average value of the separated areas of the two test pieces was determined and evaluated. At this time, when the peeling state is clean, it is excellent, when there is a trace due to the impact, and when peeling by the impact is insufficient.

-Underwater coating properties were evaluated by the strength of dropping when the test tape coated in water was cured in water and the measuring tape was removed.

-Abrasion resistance was evaluated according to ASTM D 4060 under the condition of abrasion wheel CS-17, a load of 1,000 g, and a frequency of 1,000 times, and then evaluated by the weight of the coating film lost due to abrasion.

Example 1

Water-curable modified epoxy resin (epoxy equivalent 199g/eq) 45 parts by weight, silicon carbide, alumina, titanium dioxide, calcium carbonate, mica, silica, barium sulfate and 10 parts by weight of ceramic powder containing antirust pigment, plate glass flakes (Glass Micronized glass flake of flake limited) 25 parts by weight, surfactant (SLS, SLES, ALS, ALES) 1.5 parts by weight, silane coupling agent (Silquest A187, Z-6040, KBM 403, Dynasylan GLYMO, GENIOSIL GF80, Sila-Ace S510 , G6720)} 2.5 parts by weight of other antifoaming agent, dispersing agent, leveling agent and the like were appropriately mixed to prepare a main component (a).

In addition, 85 parts by weight of a water-curable modified aliphatic amine resin (active hydrogen equivalent: 70 g/eq), 8 parts by weight of ceramic powder including silicon carbide, alumina, titanium dioxide, calcium carbonate, mica, silica, barium sulfate, and rust preventive pigment, etc. Curing component (b) was prepared by appropriately mixing additives (antifoaming agent, dispersing agent, leveling agent, etc.).

Subsequently, a coating layer 10 was formed in water with a main component (a) and a curing component (b) on an iron metal plate, and cured for 24 hours to prepare a test piece. At this time, the thickness of the coating layer 10 was 500 μm.

Comparative Example 1

It was prepared in the same manner as in Example 1, except that an epoxy resin and a bisphenol A epoxy resin were combined in place of the water-curing-modified epoxy resin, and a surfactant and a silane coupling agent were not included.

Comparative Example 2

It was prepared in the same manner as in Example 1, except that an epoxy resin and a bisphenol A epoxy resin were combined in place of the water-curing-modified epoxy resin, and a surfactant and a silane coupling agent were not included.

Table 1 shows the composition of Example 1 and Comparative Examples 1 and 2 of the present invention.

Table 2 shows the results of the water hardening performance, adhesion strength (MPa), impact strength, water coating performance, and wear resistance test results of Examples 1 and 2 of the present invention.

According to Table 1 and Table 2, the water curing performance achieved complete curing after 2 hours, 2.5 hours, and 3 hours, respectively, in Example 1 and Comparative Examples 1 and 2, respectively. This difference in water-curing performance is due to the equivalent of the water-curing-modified epoxy resin of the present invention being 190 to 210 g/eq. The adhesion strength was excellent in Example 1. However, Comparative Examples 1 and 2 exhibited relatively good adhesion. In the abrasion resistance properties, Example 1 was the best, and it was evaluated that there was no significant difference from Comparative Examples 1 and 2. In the case of impact strength, in Example 1, no peeling occurred at all in the impact strength test after water hardening, whereas in Comparative Examples 1 and 2, some peeling was confirmed. The impact strength is due to the content of plate-like glass flakes in the coating layer 10.

In the case of underwater coating performance, Example 1 was smoothly coated on the surface of the marine structure (PL) iron without the phenomenon of coating loosening or scattering in water. However, in the case of Comparative Examples 1 and 2, the phenomenon that the coating was released or scattered in water occurred. The difference in the performance of water coating is as described above in the application and content of the water-curable modified epoxy resin, surfactant and silane coupling agent components.

Above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications may be made by those skilled in the art within the scope of the technical spirit of the present invention. It is possible.

Claims (13)

The main component (a) and the curing component (b) are mixed to form a coating layer, and the main component (a) includes water-curable modified epoxy resin, ceramic powder, plate-like glass flakes and additives having an equivalent weight of 190 to 210 g/eq. The additive includes an anionic surfactant and a silane coupling agent, and the ceramic powder contains 15 to 30 parts by weight with respect to the water-curable modified epoxy resin, and the plate-shaped glass flake is 80 to 90 with respect to the water-curable modified epoxy resin Includes parts by weight, the additive comprises 1 to 5 parts by weight with respect to the coating layer,
Curing component (b) includes water-curing aliphatic amine resin and ceramic powder,
The plate-like glass flakes prevent diffusion and permeation of moisture, the average length of the long axis is 15 to 55 µm, and the average thickness is 0.1 to 0.5 µm,
The anionic surfactant is a surfactant and silane, characterized in that when the hydrophilic part dissociates in water, it becomes an anion and pushes moisture out of the surface of the marine structure by the anion at the surface of the hydrophilic part that comes into contact with moisture. Paint for underwater painting containing a coupling agent. delete The interface according to claim 1, wherein the water-curable modified epoxy resin is a bisphenol A-type epoxy resin, and optionally, at least one selected from novolac epoxy and cycloaliphatic epoxy is added. Paint for underwater painting containing an activator and a silane coupling agent. The method of claim 1, wherein the water-curable modified epoxy resin is added to at least one selected from bisphenol diglycidyl ether polymers, ethylene glycol monoethyl ether, glycyoxypropyl trimethysilane, and dicyclopentadiene polymers. A coating for water coating comprising a surfactant and a silane coupling agent, characterized in that the polar group is lowered and the molar volume is increased. According to claim 1, wherein the water-curing-type modified epoxy resin is an acid-modified polyolefin, an aqueous coating material comprising a surfactant and a silane coupling agent, characterized in that mixed. The method of claim 1, wherein the ceramic powder is silicon carbide, alumina, titanium dioxide, calcium carbonate, mica, silica, barium sulfate or at least one selected from rust-preventing pigments in water containing a surfactant and a silane coupling agent Paint for painting. delete The method of claim 1, wherein the surfactant is sulfate (sulfate), sulfonate (sulfonate), phosphate (phosphate)-based ammonia lauryl sulfate, sodium lauryl sulfate, sodium laureth sulfate, dioctylshowium sulfonate, carbohydrate A paint for water coating comprising a surfactant and a silane coupling agent, characterized in that it is at least one selected from a carboxylate, a sodium stearate, a sulfonate salt, a sulfate ester salt, and a phosphoric acid ester salt. According to claim 1, wherein the silane coupling agent is a paint for water coating comprising a surfactant and a silane coupling agent, characterized in that to hydrolyze the moisture remaining in the coating. The method of claim 1, wherein the silane coupling agent is a surfactant and a silane coupling agent, characterized in that at least any one selected from epoxy-based silane, amino-based silane, methacryoxy-based silane, chloropropyl-based silane or mercapto-based silane. Paint for underwater painting containing a. According to claim 1, The curing component of the coating (b) is a coating for water coating comprising a surfactant and a silane coupling agent, characterized in that it comprises a water-curing aliphatic amine resin that is cured even in water. According to claim 1, The coating material for water coating comprising a surfactant and a silane coupling agent, characterized in that it comprises a fiber-reinforced fiber. The interface according to claim 1, wherein the paint is applied to at least one selected from compression and resilient fabrics covering glass structures, glass tapes and glass cloths, and meshes. Paint for underwater painting containing an activator and a silane coupling agent.

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