KR102216046B1 - The coating method of anti-fouling hydrophobic coating solution - Google Patents

Abstract

The coating method using the anti-fouling hydrophobic coating solution according to the present invention for achieving the above object is a hydrophobic coating method for preventing the fixation of marine organisms on a ship's hull or marine facilities, the ship's hull or marine facilities A primer solution spraying step of spraying a primer solution consisting of isopropyl alcohol, propylene glycol monomethyl ether acetate (PGMEA), and silazane polymer, and the primer solution spraying It is characterized by consisting of a hydrophobic coating solution spraying step of spraying a hydrophobic coating solution on the hull of a ship or offshore facilities.
The coating method using the anti-fouling hydrophobic coating solution of the present invention is eco-friendly, has high antifouling properties, anticorrosive properties, transparency, etc., and has the effect of inhibiting the adhesion of various marine organisms and the growth of barnacles. In the case of coating on, the surface can be kept clean for a long time, which improves the ship's operating speed and saves energy.

Description

The coating method of anti-fouling hydrophobic coating solution

The present invention relates to a coating method using an anti-fouling hydrophobic coating solution containing nanoprotrusions, and more particularly, a high level for preventing the adhesion of marine organisms to the ship's hull or marine facilities or structures, intake pipes, fishing nets, etc. It relates to a coating method using a primer solution having antifouling and anticorrosive nanoprotrusions and a hydrophobic coating solution.

In general, after forming a biofilm in the ocean, aquatic microorganisms grow while acquiring nutrients and sharing cellular enzyme activity and metabolism with other microorganisms. To this end, it is attached to rock, concrete, artificial structures, metal surfaces, etc. to form a film and live an attached life. After initial attachment, substances such as hexane, fatty acids, and proteins, including polysaccharides, are secreted, and many biofilms are formed in the mutual process of these substances and microorganisms. It is known that larvae of marine organisms such as barnacles attach to the biofilm of these microorganisms and grow. Therefore, the adhesion of marine organisms is fundamentally attached to the bottom of the ship and reduces the speed, thereby lowering fuel efficiency or causing corrosion. In addition, the function of offshore structures may be deteriorated, or the suction pipes or pipes may be blocked, thereby causing obstacles.

Therefore, it is the current situation that the attached marine organisms are regularly removed once every several months, and the scale of the attached site is also scraped off and then painted using an antifouling paint.

In the case of existing antifouling paints, refurbishment is in progress every 4 to 6 months, and it is only one way to make it easier to remove even if seaweed or fish and shellfish stick to the surface. In other words, it is a purpose only to make the coating surface easily peeled off due to an appropriate impact by weakening the coating hardness, and thus does not have an antifouling function or a function to prevent sticking to the surface.

Therefore, there is a need to develop antifouling paints that inhibit the adhesion and growth of various marine organisms and have persistence for more than one year.

KR 10-1004283 B1 (2010. 12. 21.) KR 10-1236494 B1 (2013.02.18.)

The present invention was conceived to solve the problems of the prior art, and the problem to be solved in the present invention is to provide an anti-fouling hydrophobic coating solution having an excellent antifouling function having an effect of inhibiting the adhesion of various marine organisms and the growth of barnacles. Its purpose is to provide a used coating method.

In addition, it provides a coating method using an anti-fouling hydrophobic coating solution that maintains persistence for more than one year with only one coating, and maintains a clean surface when applied to the hull, while improving the sailing speed of the ship and saving energy. There is a purpose.

The coating method using the anti-fouling hydrophobic coating solution according to the present invention for achieving the above object is a hydrophobic coating method for preventing the fixation of marine organisms on a ship's hull or marine facilities, the ship's hull or marine facilities A primer solution spraying step of spraying a primer solution consisting of isopropyl alcohol, propylene glycol monomethyl ether Acetate (PGMEA) and silazane polymer, and the primer solution spraying It is characterized by consisting of a hydrophobic coating solution spraying step of spraying a hydrophobic coating solution on the hull of a ship or offshore facilities.

In addition, in the spraying step of the primer solution, the primer solution is propylene glycol monomethyl ether acetate (Propylene Glycol Monomethyl ether Acetate) having a purity of 80 to 99.4% based on 100 parts by weight of isopropyl alcohol having a purity of 80 to 99.9%. PGMEA)) 5 to 15 parts by weight and 0.5 to 3 parts by weight of a silazane polymer having a purity of 10 to 18% are mixed.

In addition, in the step of spraying the hydrophobic coating solution, the hydrophobic coating solution is 1 to mix and stir 1 to 10 parts by weight of a siloxane polymer and 0.1 to 10 parts by weight of a silazane polymer based on 100 parts by weight of the solvent. The primary mixing step and the dilution step of mixing and diluting the liquid mixture and the solvent mixed in the first mixing step in a ratio of 1: 5 to 10 by weight, and 0.5 to 10 parts by weight of the curing agent are mixed with respect to 100 parts by weight of the solvent. And a second mixing step of mixing the curing solution prepared in the curing solution preparation step and the diluting solution diluted in the diluting step and the curing solution prepared in the curing solution preparation step.

In addition, in the spraying step of the primer solution, the primer solution is sprayed onto the ship's hull or marine facilities at a thickness of 0.1 to 50 μm, and the spraying step of the hydrophobic coating solution is performed by hydrophobic coating on the ship's hull or marine facilities where the primer solution is sprayed. It is characterized in that the solution is sprayed with a thickness in the range of 0.1 ~ 200㎛.

The coating method using the anti-fouling hydrophobic coating solution of the present invention is for the purpose of forming nanoprotrusions, and is environmentally friendly, has high antifouling properties, anticorrosive properties, and has an effect of inhibiting the growth of barnacles and adhesion of various marine organisms, It also has a lasting more than one year, so if it is coated on the surface of the hull, the surface can be kept clean for a long time, thereby improving the ship's operating speed and reducing energy.

1 is a process flow diagram schematically showing a coating method using an anti-fouling hydrophobic coating solution according to the present invention.
2 is a process flow diagram schematically showing a method for preparing an anti-fouling hydrophobic coating solution used in the present invention.
3 is a graph showing fuel consumption and fuel economy before and after coating by applying a coating method using an anti-fouling hydrophobic coating solution prepared according to the present invention to a ship bottom.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a process flow diagram schematically showing a coating method using an anti-fouling hydrophobic coating solution according to the present invention.

The coating method using the anti-fouling hydrophobic coating solution of the present invention includes the primer solution spraying step (S10) and the hydrophobic coating solution spraying step (S20).

First, in the primer solution spraying step (S10), the primer solution is sprayed onto the ship's hull or marine facilities to a thickness of 0.1 to 50 μm.

In addition, in the step of spraying the hydrophobic coating solution (S20), the hydrophobic coating solution is sprayed to the hull or marine facilities of the ship on which the primer solution is sprayed to a thickness of 0.1 to 200 μm.

The anti-fouling hydrophobic coating method prepared according to the present invention may be selected from among a spin coating method, an immersion coating method, a curtain coating method, a sol-gel method, and a vacuum deposition method according to need, instead of the spray coating method as described above.

By forming a coating film with a thickness within the above range, it has excellent adhesion to the substrate surface, and excellent antifouling properties and anticorrosive properties can be expressed over a long period of time.

In the primer solution spraying step (S10), the primer solution,

With respect to 100 parts by weight of isopropyl alcohol having a purity of 80-99.9%, propylene glycol monomethyl ether acetate (PGMEA) having a purity of 80-99.4% is 5-15 parts by weight and a purity of 10- It is a mixture of 0.5 to 3 parts by weight of 18% silazane polymer.

More specifically, with respect to 100 parts by weight of isopropyl alcohol having a purity of 80 to 99.9%, propylene glycol monomethyl ether acetate having a purity of 80 to 99.9% (Propylene Glycol Monomethyl ether Acetate (PGMEA)) 5 to 15 parts by weight After mixing the parts and stirring for 10 to 20 minutes, 0.5 to 3 parts by weight of a silazane polymer having a purity of 10 to 18% is further mixed and stirred for 20 to 40 minutes.

In the above process, the mixtures are mixed through agitation to prevent lumps from being entangled or hardened, and to completely eliminate gases or bubbles generated during the reaction.

Propylene Glycol Monomethyl ether Acetate (PGMEA) having a purity of 80 to 99.4% is a solvent that serves to dissolve and evenly disperse each component to be mixed.

The silazane polymer functions as a binder capable of exhibiting effects such as high heat resistance, stain resistance, stain resistance, scratch prevention and corrosion prevention when prepared as a primer solution, and a silazane polymer having a purity of 10 to 15% Use.

2 is a process flow diagram schematically showing a method for preparing an anpi fouling hydrophobic coating solution used in a coating method using an anti-fouling hydrophobic coating solution according to the present invention.

The method for preparing an anti-fouling hydrophobic coating solution according to the present invention includes (i) a first mixing step, (ii) a dilution step, (iii) a curing solution preparation step, and (iv) a second mixing step.

(i) 1st mixing step

The first mixing step is a process of stirring by adding a siloxane polymer and a silazane polymer to a solvent.

More specifically, with respect to 100 parts by weight of the solvent being stirred in a stirrer, 1 to 10 parts by weight of siloxane polymer and 0.1 to 10 parts by weight of silazane polymer are added and stirred at 200 to 250 rpm for 30 to 60 minutes.

First, the solvent serves to dissolve and evenly disperse each component to be mixed. Dibutyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether , Ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate It may be composed of one or more selected from the group consisting of.

Preferably, one or two of dibutyl ether having a purity of 80 to 99.5% and propylene glycol monomethyl ether acetate having a purity of 80 to 99% may be used in combination.

The solvent used in the dilution step (S20) and the hardening solution preparation step (S30) below is also used in the same solvent as the above solvent.

The siloxane polymer functions as a coating solution to form a cured film and enhance water repellency, and a siloxane polymer having a purity of 80 to 99% is used.

The silazane polymer functions as a binder capable of exhibiting effects such as high heat resistance, stain resistance, stain resistance, scratch prevention and corrosion prevention when prepared as a coating solution, and a silazane polymer having a purity of 0.1 to 15% Use.

And, with respect to 100 parts by weight of the solvent being stirred in a stirrer, 1 to 10 parts by weight of siloxane polymer and 0.1 to 10 parts by weight of silazane polymer are added and stirred at 200 to 250 rpm for 30 to 60 minutes. This is to completely dissolve the polymer and completely remove the reaction gas generated during the mixing process.

In addition, when the reaction gas is not completely removed during the mixing process of dissolving the siloxane polymer and the silazane polymer in the solvent, micropores remain in the coating solution, thereby deteriorating the antifouling function.

Therefore, a siloxane polymer and silazane polymer are added to the solvent being stirred in a stirrer and stirred at 200 to 250 rpm for 30 to 60 minutes.

If the speed of the stirrer is stirred at less than 200 rpm, the reaction gas generated during the mixing process may not be completely removed, and if the stirring exceeds 250 rpm, it is uneconomical due to the reaction speed more than necessary.

In addition, if the stirring time is stirred for less than 30 minutes, it may be difficult to sufficiently dissolve the siloxane polymer and silazane polymer in the solvent. If the stirring time is longer than 60 minutes, the siloxane polymer and silazane polymer are sufficiently dissolved in the solvent. The reaction gas generated in the mixing process is completely removed, but the viscosity of the mixed liquid mixture increases.

(ii) Dilution step

The dilution step is a process of diluting by mixing the liquid mixture and the solvent mixed in the first mixing step.

More specifically, the liquid mixture and the solvent mixed in the first mixing step are mixed at a weight ratio of 1: 5 to 10 and diluted in a stirrer at 300 to 500 rpm for 1 to 2 hours.

Here, the solvent is the same as the solvent used in the first mixing step.

Mixing the liquid mixture and the solvent mixed in the first mixing step in a ratio of 1:5 to 10 by weight is to adjust the viscosity of the liquid mixture containing the siloxane polymer and silazane polymer in the first mixing step. .

If, in the case of mixing the liquid mixture and the solvent mixed in the first mixing step in a ratio of less than 1:5 by weight, the viscosity is high and the smoothness is lowered, resulting in poor workability during coating. In case of mixing in excess of 10, the viscosity becomes too low and the antifouling property may be lowered.

In addition, while the liquid mixture and the solvent mixed in the first mixing step are mixed at a weight ratio of 1: 5 to 10 and diluted in a stirrer at 300 to 500 rpm for 1 to 2 hours, the reaction gas generated in the dilution process is completely Is removed.

(iii) hardening solution preparation step

The step of preparing a curing solution is a process of mixing a curing agent with a solvent.

More specifically, with respect to 100 parts by weight of the solvent, 0.5 to 10 parts by weight of the curing agent is mixed in a stirrer at 200 to 250 rpm for 20 to 40 minutes.

The curing agent may be one containing one or two or more of amine-based, acid anhydride-based, polyamide-based, polyamide-amine-based, phenol-based, and carboxylic acid polyester, specifically alicyclic amine, aromatic amine, aliphatic amine And one or more selected from the group consisting of dicyandiamide, and more specifically, it is preferable to include a low-viscosity polyamine having an active hydrogen equivalent of 50 to 250.

The curing agent needs to limit the viscosity of the curing agent in order to impart eco-friendliness.

Here, when an amine having an active hydrogen equivalent of less than 50 is used, it can act as a volatile organic solvent due to high volatility, and when an amine having an equivalent amount of more than 250 is used, the coating is performed through the prepared coating solution due to high viscosity. In order to impart smoothness, a volatile organic solvent must be additionally used.

If, with respect to 100 parts by weight of the solvent, if less than 0.5 parts by weight of the curing agent is mixed, the curing speed may be slowed and curing may not be easily performed. When mixing more than 10 parts by weight, it is necessary to use more than necessary curing agent. It is economical.

(iv) 2nd mixing step

The second mixing step is a process of mixing the diluted solution diluted in the dilution step and the curing solution prepared in the curing solution manufacturing step.

More specifically, with respect to 100 parts by weight of the diluted solution diluted in the dilution step, 0.5 to 10 parts by weight of the curing solution prepared in the curing solution preparation step are mixed and stirred in a stirrer at 300 to 500 rpm for 30 to 60 minutes.

Mixing 0.5 to 10 parts by weight of the curing solution prepared in the curing solution preparation step with respect to 100 parts by weight of the diluting solution diluted in the dilution step includes silazane polymer and siloxane polymer components contained in the diluent. It is to be made into a hydrophobic coating solution with excellent adhesion by being cured by a curing agent.

When mixing less than 0.5 parts by weight of the curing solution prepared in the curing solution preparation step with respect to 100 parts by weight of the diluting solution diluted in the dilution step, curing may not be easily performed and adhesion may decrease, and exceed 10 parts by weight. In the case of mixing, the viscosity increases due to the amount of mixing more than necessary.

In addition, an additive may be further added to the mixed solution mixed in the second mixing step.

The additive may further include one or more additives selected from the group consisting of a dispersant, a surface control agent, and an antifoaming agent.

The dispersant may be an ammonium salt, an active amine, an organic acid, or an inorganic acid, and functions to modify the physical properties of the composition.

In addition, the surface control agent and the antifoaming agent are materials that function to improve the workability and productivity of the coating solution composition, and the type is not particularly limited, but preferably, a material such as acrylic type is used as the surface control agent. In addition, as the antifoaming agent, a non-silicone antifoaming agent may be used.

Here, the content of the additive may be contained in an amount of 2 to 4 parts by weight based on 100 parts by weight of the mixed solution mixed in the second mixing step.

When the additive content is less than 2 parts by weight, it is added to the diluent so that the physical properties are not sufficiently modified and workability and productivity may not be greatly improved.If the additive content exceeds 4 parts by weight, physical properties due to the addition of more than necessary This will be different.

The coating method using the anti-fouling hydrophobic coating solution having nanoprotrusions according to the manufacturing method of the present invention is eco-friendly, has excellent antifouling function, has the effect of inhibiting the adhesion of various marine organisms and the growth of barnacles, and has a persistence of more than one year. Coating on the surface of the hull can keep the surface clean for a long time, thereby improving the ship's operating speed and reducing energy.

In addition, the coating film using the anti-fouling hydrophobic coating solution prepared according to the present invention is preferably coated to a thickness in the range of 0.1 to 10 μm.

Although the preferred embodiments of the present invention have been described above, the scope of the present invention is not limited thereto, and it is to be understood that the scope of the present invention extends to the scope substantially equal to the embodiment of the present invention. Various modifications may be implemented by those of ordinary skill in the technical field to which the present invention pertains within the scope not departing from the spirit of the invention.

First, when preparing the primer solution and the anti-fouling hydrophobic coating solution of the present invention, it is prepared at room temperature of 18 to 21°C and humidity of 40% or less, and physical properties such as solvents, siloxane polymers, silazane polymers, and hardeners due to temperature and humidity. And do not cause chemical changes.

Example 1: Primer solution prepared according to the present invention

To 100 ml of isopropyl alcohol having a purity of 90%, 13 ml of propylene glycol monomethyl ether acetate (PGMEA) having a purity of 90% were mixed and stirred for 10 minutes, and then a sila having a purity of 18% 3 g of silazane polymer is mixed and stirred for 30 minutes.

Example 2: Anti-fouling hydrophobic coating solution prepared according to the present invention

1) Mixing 100 ml of dibutyl ether having a purity of 95% being stirred in a stirrer, 5 g parts by weight of a siloxane polymer having a purity of 95%, and 5 g of a silazane polymer having a purity of 15% are mixed and stirred at 200 rpm for 30 minutes.

2) 200 ml of dibutyl ether having a purity of 95% was mixed with 30 ml of the mixed liquid mixture, and diluted with a stirrer at 300 rpm for 1 hour.

3) Mix 5 g of low-viscosity polyamine having an active hydrogen equivalent of 150 to 100 ml of dibutyl ether of 95% purity, and stir in a stirrer at 200 rpm for 20 minutes.

4) Mix 3 ml of the curing solution of 3) with 50 ml of the dilution of 2) and mix with a stirrer at 300 pm for 30 minutes.

Experiment 1: Experiment of fuel economy effect before and after bottom coating

The fuel consumption and fuel consumption before and after coating were measured by applying Examples 1 and 2 manufactured according to the present invention to the bottom of a jet ski ship (fuel economy = cumulative mileage (km) / cumulative fuel consumption (L)). The results are shown in FIG. 3.

Ship tonnage: 3.2 ton

Horsepower (HP): 320 (240kW = 240kJ/s)

Tank capacity: 500L

RPM: 1,600

Via

Fuel consumption: 180 ∼ 200L/h

Usage time after one refueling

Light oil reduction: 40 ∼ 50%

Experiment 2: property evaluation

(1) Antifouling property evaluation

The primer solution (Example 1) prepared according to the present invention was sprayed onto the prepared fiberglass horizontally*vertically (30*50cm) using a spray equipment. Thereafter, after checking the state in which the sprayed primer solution was volatilized, it was sprayed twice using a spray equipment using a hydrophobic coating solution (Example 2). After drying for more than 5 hours, 3 pieces per sample were placed in the sea near the coastal police station in Pohang, Gyeongsangbuk-do, and observed and evaluated for 10 months. It was evaluated by dividing into 5 grades according to the attachment state. Comparative Example was evaluated by observing for the same place and time without treatment on the fiberglass width * length (30 * 50cm). The results are shown in Table 2 (1st grade: adhesion less than 5%, 2nd grade: adhesion 5-10%, 3rd grade: adhesion 10-30%, 4th grade: adhesion 30-50%, 5th grade: More than 50% adhesion).

As can be seen from Table 2, adhesion hardly occurred to the sample constructed according to the coating method using the anti-fouling hydrophobic coating solution having nanoprotrusions of the present invention, and in the comparative example without construction, adhesion was 50% or more. You can see that it has progressed.

Therefore, it was confirmed that the coating method using the anti-fouling hydrophobic coating solution of the present invention not only has excellent antifouling properties, but also provides an excellent antifouling effect capable of expressing the effect even when used for a long time.

(2) Product safety standard inspection

Examples 1 and 2 (primer solution and anti-fouling hydrophobic coating solution) of the present invention were evaluated as environmentally safe in addition to quality excellence through a product safety standard inspection for hazard concerns by the Korea Institute of Construction Living Environment (KCL). received.

1) Self-test number: C-A058-F00050001-A180

2) Self-test number: C-A05B-F00050002-A180

Serial number Inspection items unit Criteria test results Judgment One Formaldehyde Mg/kg 50 or less Not detected pass 2 Acetaldehyde Mg/kg 100 or less Not detected pass 3 Trichloroethylene Mg/kg 1000 or less Not detected pass 4 naphthalene Mg/kg 200 or less Not detected pass 5 Dimethylformamide Mg/kg 90 or less Not detected pass 6 benzene Mg/kg 180 or less Not detected pass 7 nickel Mg/kg below 10 Not detected pass

Claims (4)

In the hydrophobic coating method for preventing the fixation of marine organisms on the hull of a ship or marine facilities,
A primer solution spraying step of spraying a primer solution consisting of isopropyl alcohol, propylene glycol monomethyl ether acetate (PGMEA), and silazane polymer on the ship's hull or marine facilities (S10); And
A hydrophobic coating solution spraying step (S20) of spraying a hydrophobic coating solution onto the ship's hull or offshore facilities on which the primer solution has been sprayed;
Is made of,
In the hydrophobic coating solution spraying step (S20), the hydrophobic coating solution,
(i) a first mixing step of mixing and stirring 1 to 10 parts by weight of a siloxane polymer and 0.1 to 10 parts by weight of a silazane polymer based on 100 parts by weight of a solvent;
(ii) a dilution step of mixing and diluting the liquid mixture and the solvent mixed in the first mixing step at a weight ratio of 1:5 to 10;
(iii) a curing solution preparation step of mixing 0.5 to 10 parts by weight of a curing agent based on 100 parts by weight of the solvent; And
(iv) a second mixing step of mixing the diluted solution diluted in the dilution step and the curing solution prepared in the curing solution manufacturing step;
Coating method using an anti-fouling hydrophobic coating solution, characterized in that consisting of.
The method of claim 1,
In the primer solution spraying step (S10), the primer solution,
With respect to 100 parts by weight of isopropyl alcohol having a purity of 80-99.9%, propylene glycol monomethyl ether acetate (PGMEA) having a purity of 80-99.4% is 5-15 parts by weight and a purity of 10- A coating method using an anti-fouling hydrophobic coating solution, characterized in that 0.5 to 3 parts by weight of 18% silazane polymer are mixed.
delete The method of claim 1,
The primer solution spraying step (S10),
The primer solution is sprayed onto the ship's hull or marine facilities at a thickness of 0.1 to 50㎛,
The hydrophobic coating solution spraying step (S20),
Coating method using an anti-fouling hydrophobic coating solution, characterized in that spraying a hydrophobic coating solution to a hull or marine facility of a ship on which the primer solution is sprayed at a thickness ranging from 0.1 to 200 μm.

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