KR101236494B1 - Ceramic paint composition for antifouling - Google Patents

Abstract

The present invention provides an antifouling ceramic coating composition comprising an aqueous phase medium, a binder resin, an antifoaming agent, a ceramic polymer which is a reaction product of siloxane and silica, and polysilsesquioxane.
The antifouling ceramic coating composition according to the present invention has excellent antifouling property against aquatic organisms and is environmentally friendly, and can be cured at room temperature and is easy to use, and has mechanical strength, fingerprint resistance, adhesion, heat resistance, water resistance, flame resistance, acid resistance, and weather resistance. It is excellent in that it can be used as a base material coating made of materials such as iron, cast iron, stainless steel, non-ferrous metal, aluminum die-cast, glass, concrete, wood. In addition, when the antifouling ceramic coating composition according to the present invention further comprises transparent porous silica particles, it is possible to prevent glare and slipping. Therefore, the antifouling ceramic coating composition according to the present invention is very useful for marine, glass (for example, display of electronic products, lighting equipment, etc.), dark coating, construction, woodworking, and steel.

Description

Ceramic paint composition for antifouling

The present invention relates to a ceramic coating composition for antifouling, more specifically, excellent antifouling resistance to aquatic organisms, can be cured at room temperature, easy to use, mechanical strength, fingerprint, adhesion, heat resistance, water resistance, and The present invention relates to an antifouling ceramic coating composition excellent in flame resistance.

At present, paints used in various fields such as civil engineering and ships, including interior and exterior paintings of various buildings, are composed of synthetic resins, organic solvents, and pigments. However, these paints have a problem in that other harmful substances, including volatile organic compounds (VOC), are generated indispensable to the human body as well as harmful to the environment. In order to solve the above problems, ceramic paints using inorganic nonmetal materials and paints using organic and inorganic composites have been developed and marketed. However, the conventional ceramic paints are hardened at high temperatures, and thus have poor workability as compared to general organic paints, and have a problem such as contamination during construction due to a long drying time. In addition, the conventional ceramic paint has a problem in that the adhesion to the substrate is poor, the durability is lowered, and the resistance to heat, moisture, salt, and the like is inferior.

On the other hand, the bottoms, subsurface structures, fishing nets, etc., when exposed to water for a long time, animals such as barnacles, shellfish, mussels and shellfish, various aquatic organisms including plants and bacteria such as seaweed (seaweed), brown algae, red algae Surface appearance and function are likely to be impaired by surface adhesion and proliferation by seaweeds such as red algae and red algae. In particular, when these aquatic organisms adhere to and propagate on the bottom, the surface of the vessel may be roughened overall, which may reduce the speed of the vessel and increase the fuel consumed by the vessel. Excessive labor and work time are required to remove aquatic life from the bottom. In addition, when bacteria are attached to and propagated to subsurface structures, for example, mucus (mud matter) adheres to cause decay, or large cohesive organisms adhere to and proliferate on the surface of subsurface structures such as steel structures. In case of damaging the anti-corrosion coating provided on the subsurface structure, there is a risk that it may cause damage such as deterioration of strength and function of the subsurface structure and greatly shorten the life of the subsurface structure. In order to prevent such damage, a coating material having a good antifouling property, for example, a composition comprising a copolymer such as tributyltin methacrylate and methyl methacrylate and cuprous oxide (Cu ₂ O) is applied to the bottom of the ship. Is common. The copolymer of this antifouling paint was hydrolyzed in seawater to give bistributyltin oxide [Bu ₃ Sn-O-SnBu ₃ (Bu is a butyl group)] and tributyltin halide [Bu ₃ SnX (X is a halogen atom) to liberate an organotin compound such as to perform antifouling action. In addition, the copolymer hydrolyzate or the like is water-soluble as a hydrolyzable self-polishing paint and dissolved in seawater, so that the resin residue does not remain on the surface of the bottom coating, thereby maintaining an always active surface. However, the organotin compounds are very toxic, raising concerns about marine pollution, the generation of modified fish and modified shellfish, and the deleterious effects on the ecosystem through the food chain. Therefore, the development of antifouling paints containing no tin as a substitute for organotin compounds is required.

The present invention has been derived to solve the conventional problems, the object of the present invention is excellent in antifouling against aquatic organisms, environmentally friendly, and can be cured at room temperature, easy to use, mechanical strength, fingerprint, adhesion, heat resistance The present invention provides an antifouling ceramic coating composition excellent in water resistance, acid resistance, and flame resistance.

In order to solve the above object of the present invention, the present invention is 30 to 80 parts by weight of binder resin, 1 to 30 parts by weight of antifoaming agent, 5 to 30 parts by weight of ceramic polymer, and 2 to 20 polysilsesuccioxane per 100 parts by weight of the aqueous medium. Provided is an antifouling ceramic coating composition comprising a weight part.

In addition, the antifouling ceramic coating composition of the present invention may preferably further comprise a porous silica. At this time, the composition is preferably 30 to 80 parts by weight of binder resin, 1 to 30 parts by weight of antifoaming agent, 5 to 30 parts by weight of ceramic polymer, 2 to 20 parts by weight of polysilseschioxane, and porous silica 2 per 100 parts by weight of aqueous medium. And ˜20 parts by weight.

The antifouling ceramic coating composition according to the present invention has excellent antifouling property against aquatic organisms and is environmentally friendly, and can be cured at room temperature and is easy to use, and has mechanical strength, fingerprint resistance, adhesion, heat resistance, water resistance, flame resistance, acid resistance, and weather resistance. It is excellent in that it can be used as a base material coating made of materials such as iron, cast iron, stainless steel, non-ferrous metal, aluminum die-cast, glass, concrete, wood. In addition, when the antifouling ceramic coating composition according to the present invention further comprises transparent porous silica particles, it is possible to prevent glare and slipping. Therefore, the antifouling ceramic coating composition according to the present invention is very useful for marine, glass (for example, display of electronic products, lighting equipment, etc.), dark coating, construction, woodworking, and steel.

Hereinafter, the present invention will be described in detail. The antifouling ceramic coating composition according to the present invention includes an aqueous medium, a binder resin, an antifoaming agent, a ceramic polymer which is a reaction product of siloxane and silica, and polysilsesquioxane. In addition, the antifouling ceramic coating composition according to the present invention may preferably further comprise a porous silica. The antifouling ceramic coating composition according to the present invention will be described by dividing the composition into components.

Water medium

The aqueous phase serves as a dispersion medium for dispersing the ceramic polymer, polysilsesquioxane, or porous silica, the reaction product of siloxane and silica. In the present invention, the aqueous medium is not limited as long as it is a liquid material compatible with water as well as water, specifically, any one selected from the group consisting of water, alcohol having 1 to 5 carbon atoms and mixtures thereof. Can be. In this case, the alcohol having 1 to 5 carbon atoms is not limited to methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol and the like, and is preferably selected from ethanol, propanol, isopropanol, butanol, isobutanol and the like. Do.

Binder resin

The binder resin serves to form a film when applying the antifouling ceramic coating composition according to the present invention, and serves to provide adhesion to the film. In the present invention, the binder resin is not limited in kind, and for example, a fluorine resin, an acrylic resin, a vinyl chloride resin, a copolymer of vinyl chloride and vinyl acetate, a copolymer of styrene and butadiene, a polyester, an epoxy resin, and a phenol resin It may be composed of one or more selected from the group consisting of polyolefin, polyamide, and polyurethane. In the present invention, the binder resin is preferably selected from an epoxy resin or a polyurethane, and more preferably a polyurethane, in consideration of curing properties, film forming ability, adhesion, and the like. The content of the binder resin in the antifouling ceramic coating composition according to the present invention is not particularly limited, but considering the uniform mixing of the antifouling ceramic coating composition, curing properties, curing properties, film forming ability, adhesion, etc. It is preferable that it is 30-80 weight part per weight part, It is more preferable that it is 40-70 weight part, It is most preferable that it is 50-60 weight part.

Antifoam

Defoaming agent (defoaming agent) by applying the antifouling ceramic coating composition according to the invention serves to prevent the occurrence of bubbles when forming a film to form a uniform film and serves to provide elasticity to the film. In the present invention, if the antifoaming agent is a general antifoaming agent used for coating, the type thereof is not particularly limited and is exemplified in "21 CFR (Code of Federal Regulations) 176.200-Defoaming agents used in coatings." Antifoaming agent in the present invention, considering the compatibility with other components, preferably polyethylene glycol dilaurate (Polyethylene glycol dilaurate), polyethylene glycol monooleate (Polyethylene glycol monooleate), polyethylene glycol dioleate (Polyethylene glycol dioleate) ), Polyethylene glycol monoricinoleate, polyethylene glycol monostearate, polyoxypropylene oleate butyl ether, and polyoxypropylene stearate butyl ether Stearate butyl ether) may be composed of one or more selected from the group consisting of, more preferably polyoxypropylene oleate butyl ether (polyoxypropylene oleate butyl ether), or polyoxypropylene stearate butyl ether (Polyoxypropylene s tearate butyl ether) may be composed of one or more selected from. In the antifouling ceramic coating composition according to the present invention, the content of the antifoaming agent is not particularly limited, but considering the anti-foaming characteristics and economical efficiency, it is preferable that it is 1-30 parts by weight, and 3-25 parts by weight per 100 parts by weight of the aqueous medium. It is more preferable, and it is most preferable that it is 5-20 weight part.

ceramic Polymer

In the present invention, the ceramic polymer is a reaction product of siloxane and siloxane, and serves to provide mechanical strength to a film formed by applying the antifouling ceramic coating composition according to the present invention. At this time, the siloxane is not greatly limited in its kind, such as cyclic siloxane (Cyclic siloxanes), linear siloxane (Linear siloxanes), hexamethylcyclotrisiloxane when considering the mechanical strength and compatibility with other components, etc. Cyclic siloxane consisting of one or more selected from the group consisting of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. (Cyclic siloxanes) is preferable. Commercial products of the ceramic polymer used in the present invention include CAS No. 68583-50-6 (reaction product of hexamethylcyclotrisiloxane and silica), CAS No. 68583-49-3 (octamethylcyclotetrasiloxane) Reaction products of silica). The content of the ceramic polymer in the antifouling ceramic coating composition according to the present invention is not particularly limited, but considering the uniform mixing and mechanical strength of the antifouling ceramic coating composition, it is preferably 5 to 30 parts by weight per 100 parts by weight of the aqueous medium. It is more preferable that it is 10-25 weight part, and it is most preferable that it is 15-20 weight part.

Polysilsesuccioxane

Polysilsesuccioxane is provided by imparting antifouling properties against aquatic organisms to the antifouling ceramic coating composition according to the present invention, enabling room temperature curing of the antifouling ceramic coating composition according to the present invention, and coating the antifouling ceramic coating composition. It serves to improve the mechanical strength, fingerprint resistance, heat resistance, water resistance, flame resistance, acid resistance, and weather resistance of one film, and also serves to improve transparency. Poly silsesquioxane in the present invention has a T unit structures represented by _{RSiO 3/2 (RSiO 3/} 2) if the polymer is represented by _n is not the type is severely limited, wherein the substituent R is an alkyl group (alkyl), alkyl It is any one selected from an alkylene, an aryl group, an arylene group, and their derived organic functional groups. In addition, polysilsesukioxane used in the present invention includes those disclosed in Korean Patent Laid-Open Publication No. 2000-0063142. On the other hand, the polysilsesukioxane used in the present invention is polymethylsilsesquioxane (polymethylsilsesquioxane, PMSQ), polyphenylsilsesquioxane (polyphenylsilsesquioxane, PPSQ), and poly considering the compatibility with other components and availability It is preferably composed of one or more selected from the group consisting of hydrogensyl seskioxane (polyhydrogensilsesquioxane, PHSQ). In the antifouling ceramic coating composition according to the present invention, the content of polysilsesukioxane is not limited. However, the antifouling, mechanical strength, anti-fingerprint, heat resistance, water resistance, flame resistance, and acid resistance of the coating film formed by applying the antifouling ceramic coating composition And 2 to 20 parts by weight, more preferably 3 to 15 parts by weight, per 100 parts by weight of the aqueous medium, in consideration of weather resistance and the like.

Porous silica

The antifouling ceramic coating composition according to the present invention may preferably further comprise porous silica. Porous silica imparts an anti-slip function and an anti-glare function to the film formed by applying the antifouling ceramic coating composition. The type of porous silica is not particularly limited and includes, for example, silica gel, silica fume, or silica formed from a sol-gel process using silicate as a raw material. The porous silica is preferably transparent when considering anti-glare characteristics of the coating film formed by applying the antifouling ceramic coating composition. In addition, the porous silica is in the form of particles having a particle size of 20 to 2000 in consideration of compatibility with other components, dispersibility in the composition, or the anti-slip properties of the coating formed by applying the antifouling ceramic coating composition. It is preferable that it is preferable and it is a particle form which has a particle diameter of 30-1000. In addition, the average pore size of the porous silica is preferably 0.5 to 10 and more preferably 1 to 5 in consideration of anti-glare characteristics of the coating film formed by applying the antifouling ceramic coating composition. The content of the porous silica in the antifouling ceramic coating composition according to the present invention is not significantly limited, but the anti-slip and anti-glare characteristics of the coating film formed by uniform mixing of the antifouling ceramic coating composition or by applying the antifouling ceramic coating composition It is preferable that it is 2-20 weight part with respect to 100 weight part of aqueous media, and, as for consideration, etc., it is more preferable that it is 3-15 weight part.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples merely illustrate the present invention more clearly and do not limit the protection scope of the present invention.

One. Antifouling  Preparation of Ceramic Paint Composition

Example  One.

100 parts by weight of water, 40 parts by weight of polyurethane, 10 parts by weight of 32% polyoxypropylene oleate butyl ether solution (CAS reg. No .: 37281-78-0), reaction product of octamethylcyclotetrasiloxane and silica (CAS registration No. 68583-49-3) 10 parts by weight of a ceramic polymer and 2 parts by weight of polymethylsilsesquioxane (PMSQ) were mixed and stirred to prepare a ceramic antifouling composition.

Example  2.

100 parts by weight of water, 60 parts by weight of polyurethane, 50 parts by weight of 32% polyoxypropylene oleate butyl ether solution (CAS reg. No .: 37281-78-0), reaction product of octamethylcyclotetrasiloxane and silica (CAS registration) No. 68583-49-3) 20 parts by weight of a ceramic polymer and 10 parts by weight of polymethylsilsesquioxane (PMSQ) were mixed and stirred to prepare a ceramic antifouling composition.

Example  3.

100 parts by weight of water, 40 parts by weight of polyurethane, 10 parts by weight of 32% polyoxypropylene oleate butyl ether solution (CAS reg. No .: 37281-78-0), reaction product of octamethylcyclotetrasiloxane and silica (CAS registration No. 68583-49-3) 10 parts by weight of a ceramic polymer, 2 parts by weight of polymethylsilsesquioxane (PMSQ), and a transparent porous silica (particle size ranged from 100 to 1000, with an average pore size of about 2.5 2) by weight of 2 parts by mixing and stirring to prepare an antifouling ceramic coating composition.

Example  4.

100 parts by weight of water, 60 parts by weight of polyurethane, 50 parts by weight of 32% polyoxypropylene oleate butyl ether solution (CAS reg. No .: 37281-78-0), reaction product of octamethylcyclotetrasiloxane and silica (CAS registration) No. 68583-49-3) 20 parts by weight of a ceramic polymer, 10 parts by weight of polymethylsilsesquioxane (PMSQ), and transparent porous silica (particle size ranged from 100 to 1000, with an average pore size of about 2.5 10 parts by weight of the mixture) and stirred to prepare an antifouling ceramic coating composition.

Comparative example  One.

100 parts by weight of water, 40 parts by weight of polyurethane, 10 parts by weight of 32% polyoxypropylene oleate butyl ether solution (CAS reg. No .: 37281-78-0), and the reaction product of octamethylcyclotetrasiloxane and silica (CAS Registration number: 68583-49-3) 10 parts by weight of a ceramic polymer was mixed and stirred to prepare an antifouling ceramic coating composition.

Comparative example  2.

100 parts by weight of water, 60 parts by weight of polyurethane, 50 parts by weight of 32% polyoxypropylene oleate butyl ether solution (CAS reg. No .: 37281-78-0), and a reaction product of octamethylcyclotetrasiloxane and silica (CAS Registration number: 68583-49-3) 20 parts by weight of a ceramic polymer was mixed and stirred to prepare an antifouling ceramic coating composition.

2. Antifouling  Characterization of Ceramic Coating Compositions

(1) antifouling evaluation

The antifouling ceramic coating composition prepared in Examples 1 to 4 and the antifouling ceramic coating composition prepared in Comparative Examples 1 to 2 were applied to the specimen steel sheet and cured at a high temperature to form a film of about 100.

The coated steel sheet was placed at a depth of 1 m in the sea, and after 1 year, the adhesion area of the barnacle was evaluated, and the results are shown in Table 1.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Score 4 5 4 5 One One

In Table 1, "valuation score criteria" are as follows.

5: no attachment; 4: adhesion is less than 5%; 3: adhesion is at least 5% and less than 20%; 2: adhesion is at least 20% and less than 50%; 1: 50% or more of attachment

(2) evaluation of other characteristics

The items shown in Table 2 below were evaluated for the antifouling ceramic coating compositions prepared in Examples 1 to 4.

Evaluation items Assessment Methods Example 1 Example 2 Example 3 Example 4 Drying time KS M 5000 (2009) 30 minutes 25 minutes 24 minutes 23 minutes Curing and Drying Time KS M 5000 (2009) 60 minutes 54 minutes 49 minutes 48 minutes Pencil hardness KS M ISO 15184 (2002) 3H 4H 4H 5H Adhesion KS D 6711 (1992) 100/100 100/100 100/100 100/100 Heat resistance test Peel off after 80 ± 2, 2hr clear clear clear clear A cold exam -20 ± 2, Peel off after 24hr clear clear clear clear Peel off after repeated high temperature and low temperature (-20 ± 2, 1hr room temperature, 1h 80 ± 2, 1h room temperature, 1h) Peel off after 2 Cycles clear clear clear clear Moisture resistance KS D 6711 (1992): 40 ± 1, 75% RH, swelling after 24hr clear clear clear clear Salt spray test KS D 9502 (2009): Swelling after 150hr clear clear clear clear Immersion test KS M ISO 2812-1 (2007): 10% hydrochloric acid, swelling after 10 minutes at room temperature clear clear clear clear

As shown in Table 2, the antifouling ceramic coating composition according to the present invention has a dry touch time of 30 minutes or less, a curing dry time at room temperature of 1 hour or less, and easily forms a film, and the formed film has adhesion, heat resistance, It was excellent in cold resistance, durability, moisture resistance, flame resistance, and acid resistance.

Although the present invention has been described through the above embodiments as described above, the present invention is not necessarily limited thereto, and various modifications can be made without departing from the scope and spirit of the present invention. In addition, many modifications may be made to adapt a particular situation and material to the teachings of the invention without departing from the essential scope thereof. Accordingly, the protection scope of the present invention should not be construed as being limited to the particular embodiments disclosed as the best mode contemplated for carrying out the invention but to cover all embodiments falling within the scope of the appended claims.

Claims (12)

A composition comprising 30 to 80 parts by weight of binder resin, 1 to 30 parts by weight of antifoam, 5 to 30 parts by weight of ceramic polymer, and 2 to 20 parts by weight of polysilsesuccioxane per 100 parts by weight of the aqueous medium,
The ceramic polymer is an antifouling ceramic coating composition, characterized in that the reaction product of siloxane (siloxane) and silica. The method of claim 1,
The composition is an antifouling ceramic coating composition further comprises a porous silica. The method of claim 2,
The composition is 30 to 80 parts by weight of binder resin, 1 to 30 parts by weight of antifoam, 5 to 30 parts by weight of ceramic polymer, 2 to 20 parts by weight of polysilseschioxane, and 2 to 20 parts by weight of porous silica per 100 parts by weight of the aqueous medium. An antifouling ceramic coating composition, comprising: 4. The method according to any one of claims 1 to 3,
The aqueous phase medium is any one selected from the group consisting of water, alcohols having 1 to 5 carbon atoms, and mixtures thereof. 4. The method according to any one of claims 1 to 3,
The binder resin is a group consisting of fluorine resin, acrylic resin, vinyl chloride resin, copolymer of vinyl chloride and vinyl acetate, copolymer of styrene and butadiene, polyester, epoxy resin, phenol resin, polyolefin, polyamide, and polyurethane Ceramic coating composition for antifouling, characterized in that composed of one or more selected from. 4. The method according to any one of claims 1 to 3,
The antifoaming agent is polyethylene glycol dilaurate, polyethylene glycol monooleate, polyethylene glycol dioleate, polyethylene glycol monoricinoleate, polyethylene One or more selected from the group consisting of glycol glycol monostearate, polyoxypropylene oleate butyl ether, and polyoxypropylene stearate butyl ether An antifouling ceramic coating composition characterized by the above-mentioned. 4. The method according to any one of claims 1 to 3,
Siloxane forming the ceramic polymer is cyclic siloxane, characterized in that the ceramic coating composition for antifouling. 8. The method of claim 7,
The cyclic siloxane is from the group consisting of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Ceramic coating composition for antifouling, characterized in that composed of one or more selected. 4. The method according to any one of claims 1 to 3,
The polysilseschioxane is at least one selected from the group consisting of polymethylsilsesquioxane (PMSQ), polyphenylsilsesquioxane (PPSQ), and polyhydrogensilsesquioxane (PHSQ). Ceramic coating composition for antifouling, characterized in that configured. 4. The method according to claim 2 or 3,
The porous silica coating composition, characterized in that the porous silica is transparent. 4. The method according to claim 2 or 3,
The porous silica is an antifouling ceramic coating composition, characterized in that the particle form having a particle diameter of 20 ~ 2000nm. 4. The method according to claim 2 or 3,
The average pore size of the porous silica is a ceramic coating composition for antifouling, characterized in that 0.5 ~ 10nm.