KR101854047B1 - Antifouling paint compositions - Google Patents

Abstract

The present invention provides an antifouling paint composition comprising a siloxane-urethane copolymer and a hydrolysable functional group containing oligomer or prepolymer containing at least one of a metal or silyl group. The siloxane-urethane copolymer can be a copolymer of chemical formula 1, wherein R_1 is H or CH_3.

Description

[0001] Antifouling paint compositions [0002]

The present invention relates to an antifouling paint composition.

(Especially at the bottom of the ship), fishing nets such as fishing nets, fishing nets, fishing nets, fishing nets, etc., and power plant water pipes, etc. , The fuel cost, which accounts for a large part of the operational expenses, can be greatly increased, the function of the ship is impaired, and the appearance is damaged.

Therefore, an antifouling paint composition to which an antifouling resin is applied is intended to prevent or control the adhesion and growth of the above marine organisms causing surface contamination of a coating film on which seawater is deposited. When various marine organisms are attached to the surface of the film, the frictional force between the surface of the coating and the sea surface increases during the operation of the tillage of the ship, which can increase the fuel cost, which is a large part of the operating expenses. The antifouling paint is a paint for preventing the formation of such adherence and reducing the coefficient of friction between seawater and the ship during operation.

Antifouling paints are antifouling paints that exhibit antifouling performance by dissolving antifouling agents such as ash antioxidants as the resin in the film is hydrolyzed, and antifouling paints that exhibit antifouling performance by reducing the surface tension of marine copper / have.

Among these, the Foul-Release type which exhibits the antifouling performance by lowering the surface tension has a great advantage of being environmentally friendly and exhibiting its effect semi-permanently, however, when the ship is maintained at a constant speed or more, , It is difficult to recover the contaminated parts once again. In order to overcome this problem, fluorine - denatured additives were applied to the surface of the coated film to improve the antifouling performance of the cured polysiloxane - coated film. However, contamination due to old stagnation period or low speed operation still remains as a problem that can not be recovered easily.

The present invention provides an antifouling paint composition.

The present invention provides a composition for an antifouling paint comprising a siloxane-urethane copolymer and a hydrolyzable functional group-containing oligomer or prepolymer containing at least one of a metal and a silyl group.

The siloxane-urethane copolymer may be a copolymer of the following formula (1).

[Chemical Formula 1]

Wherein R ₁ is H or CH ₃ and R ₂ is an aliphatic group, alicyclic group or aromatic group of C ₂ or more and R ₃ is a direct bond or a C ₁ to C ₁₅ aliphatic group, R ₄ is a direct bond or a C ₁ to C ₁₅ aliphatic group, R ₅ is a direct bond, or (a C _a H _2a O) _b , wherein a = 1 to 4, b = 1 to 10 _, R ₆ to R ₁₀ are C ₁ to C ₈ aliphatic, alicyclic or aromatic groups, n is 0 to 5, and m is 5 to 200.

The hydrolyzable functional group-containing oligomer or prepolymer may be one comprising a repeating unit derived from the following formula (2) or (3).

(2)

(3)

Wherein R ₁₁ is H, CH ₃ and R ₁₂ are C ₁ to C ₃₀ aliphatic, alicyclic or aromatic groups, R ₁₃ is H, CH ₃ and R ₁₄ to R ₁₆ are each C ₁ to C an aliphatic group, an alicyclic group, an aromatic group of _20, wherein Me may be one selected from the group consisting of Zn, Cu, Mo and Co.

According to the present invention, it is possible to provide a composition for an antifouling paint excellent in the synthesis stability and excellent in storage stability and long-term antifouling performance.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example only, and not limitation.

It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise.

In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Therefore, the constitution shown in the embodiments described herein is merely a preferred embodiment of the present invention, and does not represent all the technical ideas of the present invention, so that various equivalents and substitutes There may be variations.

As used herein, the term "parts by weight " means the weight ratio between the raw material components.

The composition for an antifouling paint of the present invention may comprise a siloxane-urethane copolymer and a hydrolyzable functional group-containing oligomer or prepolymer containing at least one of a metal or silyl group.

<Siloxane-urethane Copolymer>

The siloxane-urethane copolymer of the present invention may be represented by the following formula (1).

[Chemical Formula 1]

The siloxane-urethane copolymer of formula (1) may be a copolymer formed by copolymerization of a monomer containing an isocyanate group and a polymerizable double bond, and a monomer containing a hydroxyl group and a silicon group. In addition, the siloxane-urethane copolymer may have a solid content of 10 to 70%.

Wherein R ₁ is H or CH ₃ and R ₂ is an aliphatic group, alicyclic group or aromatic group of C ₂ or more and R ₃ is a direct bond or a C ₁ to C ₁₅ aliphatic group, R ₄ is a direct bond or a C ₁ to C ₁₅ aliphatic group, R ₅ is a direct bond, or (a C _a H _2a O) _b , wherein a = 1 to 4, b = 1 to 10 _, R ₆ to R ₁₀ are C ₁ to C ₈ aliphatic, alicyclic or aromatic groups, n is 0 to 5, and m is 5 to 200.

The siloxane-urethane copolymer may be contained in an amount of 10 to 70 parts by weight based on the solid content in the antifouling paint composition. When the content of the siloxane-urethane copolymer is less than 10 parts by weight, the surface tension of the coating composition is not sufficiently lowered and the antifouling property is not good. When the content of the siloxane-urethane copolymer exceeds 70 parts by weight, Etc. may not be good.

The monomer having an isocyanate group and a polymerizable double bond may be specifically an oligomer or a prepolymer of the following formula (1a).

[Formula 1a]

Here, R ₁ to R ₃ and n may be the same as those defined in the above-described formula (1).

The monomer containing a hydroxyl group and a silicon group may be an oligomer or a prepolymer of the following formula (1b), which is capable of exhibiting an antifouling performance while lowering the surface tension by being polymerized at the end of the polymer.

[Chemical Formula 1b]

Here, R ₄ to R ₁₀ and m may be the same as those defined in the above-mentioned formula (1).

The monomer containing the isocyanate group and the polymerizable double bond, and the monomer containing the hydroxyl group and the silicon group may be copolymerized at a molar ratio of 0.9: 1.1 to 1.1: 0.9.

&Lt; Hydrolyzable functional group-containing oligomer or prepolymer &

The hydrolyzable functional group-containing oligomer or prepolymer containing at least one of the metal or silyl groups of the present invention may be one comprising a repeating unit derived from the following general formula (2) or (3). When the coating film is brought into contact with the seawater after the coating film is formed by using the antifouling paint composition, the oligomer or prepolymer containing the hydrolyzable functional group is hydrolyzed and the coating film is peeled off and the new coating film is regenerated The antifouling performance can be maintained continuously. The hydrolyzable functional group-containing oligomer or prepolymer of the present invention may have a solid content of 20 to 70%.

(2)

(3)

Wherein R ₁₁ is H or CH ₃ and R ₁₂ is a C ₁ to C ₃₀ aliphatic group, alicyclic group or aromatic group, R ₁₃ is H or CH ₃ , and R ₁₄ to R ₁₆ are each C ₁ to C ₂₀ aliphatic group, alicyclic group, or aromatic group, and Me may be selected from the group consisting of Zn, Cu, Mo, and Co.

The hydrolyzable functional group-containing oligomer or prepolymer may be contained in an amount of 10 to 90 parts by weight based on the solid content in the antifouling paint composition. If the content of the hydrolyzable functional group-containing oligomer or prepolymer is less than 10 parts by weight, the surface tension of the coating composition is not sufficiently lowered and the antifouling property is not good. If the content of the oligomer or prepolymer containing hydrolyzable functional groups exceeds 90 parts by weight, The stain resistance after application to the member may not be good.

The present invention simultaneously contains the hydrolyzable functional group-containing oligomer or prepolymer containing at least one of the siloxane-urethane copolymer and the metal or silyl group in the antifouling paint composition as described above to improve the storage stability of the antifouling paint composition itself and the long- But also the synthesis stability can be ensured.

Examples of the polymerization method of the siloxane-urethane copolymer include solution polymerization bulk polymerization, emulsion polymerization, suspension polymerization and the like. In the polymerization reaction, an organic solvent may be used if necessary, so long as it does not affect the reaction. Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; Aliphatic hydrocarbon solvents such as hexane and heptane; Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate; Ether solvents such as dioxane, diethyl ether and dibutyl ether; And ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. However, since the alcohol-based solvent may participate in the polymerization reaction, it is not applied until the polymerization reaction of the siloxane-urethane copolymer is completed. According to one embodiment of the present invention, a hydrocarbon solvent or xylene can be used. These solvents may be used alone or in combination of two or more.

The polymerization reaction may be conducted under an inert gas atmosphere such as nitrogen gas or argon gas.

The siloxane-urethane copolymer may be subjected to a urethane reaction with an isocyanate group and a monomer containing a polymerizable double bond and a monomer containing a hydroxyl group and a silicon group before the polymerisation (radical) reaction, . At this time, alcohol solvent is not applied. Alternatively, monomers containing a hydroxyl group and a silicon group, a metal and a low molecular weight compound after the polymerization reaction of a monomer containing an isocyanate group and a polymerizable double bond, a hydrolyzable monomer, and a monomer containing a polymerizable double bond, Or by reacting an organic acid.

The antifouling paint composition according to the present invention can be prepared by blending an antifouling agent, an elution regulator, a plasticizer and other resins as necessary. Thereby, a more excellent antifouling effect can be exhibited.

<Other additives>

The antifouling paint composition of the present invention may further contain additives such as pigments, dyes, antifoaming agents, flow inhibitors, dispersants, anti-settling agents, dehydrating agents and organic solvents in a suitable coating film speed and coating film properties It can be added to the extent that it is not damaged.

Examples of the pigment include zinc oxide, red iron oxide (Bengala), talc, titanium oxide, silica, calcium carbonate, barium sulfate, calcium oxide, magnesium oxide and the like. These may be used alone or in combination of two or more.

As the dye, various organic dyes soluble in organic solvents and the like can be mentioned.

Examples of antifoaming agents include silicone resin antifoaming agents and acrylic resin antifoaming agents.

Examples of the anti-flow agent, dispersant or anti-settling agent include fatty acid amide wax, polyethylene oxide and the like.

Examples of the dehydrating agent include silicates and isocyanates such as synthetic zeolite adsorbents, ortho esters, and tetraethoxysilane. These may be used alone or in combination of two or more.

Examples of the organic solvent include those usually compounded in an antifouling paint such as an aliphatic solvent, an aromatic solvent, a ketone solvent, an ester solvent and an ether solvent. These may be used alone or in combination of two or more.

The antifouling paint composition of the present invention can be produced by mixing and dispersing the above-mentioned composition for an antifouling paint, a mixed solution containing an antifouling agent, an elution regulator, a plasticizer and the like using, for example, a dispersing machine. As the solvent, the same organic solvent as mentioned above can be used.

As the disperser, for example, those that can be used as a fine pulverizer can be used suitably. For example, a commercially available homomixer, sand mill, bead mill, or the like can be used. The above mixed liquid may be mixed and dispersed by adding glass beads or the like for mixed dispersion to a container provided with a stirrer.

&Lt; Antifouling treatment method, antifouling coating film and coating material >

The antifouling paint composition according to the present invention can be applied to various coated film formulations requiring an antifouling function, and can be applied to, for example, a ship (especially a ship bottom), a fishing tool, an underwater structure and the like. Examples of fishing equipment include fishing nets for aquaculture or stationary use, fishing nets for fishing nets, fishing nets such as ropes, and the like. Examples of underwater structures include power plants, bridges, harbors, Equipment and the like.

Examples of the method of applying the antifouling paint composition according to the present invention to the surface (all or a part of the surface) of the coating film formation include a brush coating, a spraying method, a dipping method, a flow coating method and a spin coating method . These may be used alone or in combination of two or more. The applied antifouling paint composition is dried through a drying process, for example, it may be dried at room temperature. The drying time may be suitably set in accordance with the thickness of the coating film or the like.

The thickness of the antifouling coating film of the present invention may be suitably set in accordance with the kind of the coating film formation, the speed of the ship, the sea water temperature, and the like. For example, when the coated film is the bottom of a ship, the thickness of the antifouling coating film is usually 50 to 500 占 퐉 or 100 to 400 占 퐉.

Since the coating material of the present invention has a coating film excellent in long-term stable surface renewal and recoatability by improving the coating film dissolution rate and coating film property in seawater, it is possible to provide a coating film for a water- Can be suitably used. For example, when the antifouling coating film is formed on the bottom surface of a ship, the antifouling coating film slowly dissolves on the surface to always renew the surface of the coating film, thereby preventing attachment of aquatic organisms. In addition, the hydrolysis rate of the antifouling coating film may be appropriately suppressed. Therefore, the ship can maintain the antifouling performance for a long period of time. For example, there is almost no adherence or accumulation of aquatic organisms even in an anchoring state or during a standing state during the fitting period, Can be exercised.

Further, even after elapse of a long time, cracks and peeling are basically not generated in the antifouling coating film on the surface. Therefore, it is not necessary to perform a work such as forming the coating film once again after completely removing the coating film. Therefore, by directly coating the antifouling coating film composition, an antifouling coating film can be suitably formed. Therefore, the antifouling performance can be maintained easily and continuously.

Example  And Comparative Example

Hereinafter, the features of the present invention will be clarified with examples and the like. However, the present invention is not limited to these embodiments.

&Lt; Preparation of composition >

Example 1

(Toluene) was added to a four-necked flask equipped with a stirrer, a thermometer and a condenser under a nitrogen atmosphere, and the mixture was heated to 110 DEG C and refluxed. The monomer mixture liquid and the first initiator shown in Table 1 were added dropwise uniformly for 4 hours, and the reflux was maintained for 1 hour, and then the second initiator was added dropwise for 10 minutes (hereinafter, the unit in the table is grams (g)). ). After maintaining the reflux for 2 hours, the silicone monomer is added dropwise for 10 minutes and reflux is maintained for 5 hours. After cooling to 60 ° C, the hydrolysis monomer is injected and heated to reflux (100 ° C) for 5 hours.

 Example 2

 (Toluene) was added to a four-necked flask equipped with a stirrer, a thermometer and a condenser under a nitrogen atmosphere, and the mixture was heated to 110 DEG C and refluxed. Then, the monomer mixture solution and the first initiator shown in Table 1 were added dropwise uniformly for 4 hours, maintained at reflux for 1 hour, added dropwise with a second initiator for 10 minutes, and refluxed for 1 hour. The third initiator is added dropwise for 10 minutes and then maintained for 2 hours. Then, the silicone monomer shown in Table 1 was added dropwise for 10 minutes, and reflux was maintained for 5 hours.

Comparative Example 1

(Toluene) was added to a four-necked flask equipped with a stirrer, a thermometer and a condenser under a nitrogen atmosphere, and the mixture was heated to 110 DEG C and refluxed. The monomer mixture liquid and the first initiator shown in Table 1 were added dropwise uniformly for 4 hours, maintained at reflux for 1 hour, and then the second initiator was added dropwise for 10 minutes. After refluxing for 2 hours, the mixture was cooled to 60 ° C, the hydrolysis monomer shown in Table 1 was poured therein, and the mixture was heated to reflux (100 ° C) for 5 hours.

division Raw material Example 1 Example 2 Comparative Example 1 Initial solvent Toluene 320 300 350 Monomer mixture MMA 194 228 163 EA 88 50 MAA 70 88 TIPX 300 2-MEA 60 PEGMEMA 40 50 IEA 8 12 SMA 150 Primary initiator TAPO 64 1.2 80 Toluene 160 120 150 Secondary initiator TAPO 0.8 0.6 One Toluene 40 60 50 Tertiary initiator TAPO 0.6 Toluene 60 silicon CMS 159 239 Toluene 40 262 The hydrolyzable monomer N / A 180 225 ZnO 66 83 n-BuOH 220 225 DIW 15 18

MMA: Methyl methacrylate

EA: Ethyl acrylate

MAA: Methacrylic acid

TIPX: triisopropyl silyl acrylate

PEGMEMA: polyethylene glycol (400) monomethyl ether methacrylate

IEA: Isocyanato ethyl acrylate

SMA: Silicone modified acrlyate

CMS:: Carbinol modified silicone

TAPO: tert-amyl peroxy-2-hexanoate

N / A: Naphthenic acid

ZnO: Zinc oxide

n-BuOH: n-butanol

DIW: de-ionized water

<Evaluation of Composition>

The properties of the compositions prepared in Examples and Comparative Examples were evaluated. The results are shown in Table 2.

Assessment Methods

① Solid content measurement

1 g of the composition prepared in Examples and Comparative Examples was taken and heated at 150 캜 for 30 minutes. The solid content (%) was calculated as the weight of the sample after heating / the weight of the sample before heating × 100 (%).

② Viscosity

The compositions of the Examples and Comparative Examples were measured at 25 캜 by a Gardner viscometer.

③ Tea occurrence

The compositions of the examples and the comparative examples were observed after the filter and the remnants in the filter and the remnants in the flask.

④ Storability

The compositions of the examples and comparative examples were stored at 60 占 폚 and then the outer appearance was observed to confirm whether or not the layers were separated.

Item Example 1 Example 2 Comparative Example 1 Solids 50.4% 50.5% 50.5% Viscosity X U Z Tee occurrence none none Occur Shelf life (60 ℃) 1 week - - - Two weeks - - Layer separation Three weeks - - Layer separation

&Lt; Preparation of antifouling paint composition >

An antifouling paint composition was further prepared by further including the substances having the composition and contents described in Table 3 below in the compositions prepared in the above Examples and Comparative Examples.

varnish Example 3 Example 4 Comparative Example 2 Example 1 40 Example 2 40 Comparative Example 1 40 Bengala 5 5 5 Titanium bag 5 5 5 Zinc oxide 10 10 10 Talc 5 5 5 Amide wax 2 2 2 Xylene 28 28 28

<Evaluation of Composition>

The physical properties of the antifouling paint compositions prepared in Examples and Comparative Examples were evaluated. The results are shown in Table 4.

Assessment Methods

① Solid content

 1 g of the antifouling paint composition prepared in Examples and Comparative Examples was taken and heated at 150 캜 for 30 minutes. The solid content (%) was calculated as the weight of the sample after heating / the weight of the sample before heating × 100 (%).

② Viscosity

The antifouling paint compositions of Examples and Comparative Examples were measured at 25 占 폚 using Kreb's unit.

③ Storage

The antifouling paint compositions of the examples and comparative examples were stored at 60 占 폚 for one week and then viscosities were measured under the conditions of ② viscosity measurement.

④ Antifouling performance

The antifouling performance was measured under the following conditions.

Ⅰ Specimen: 550 × 150 × 2 (mm) Steel plate

Ⅱ Specimen treatment: Sandblasting → Epoxy system paint 200 ㎛ → Epoxy binder paint 100 ㎛ (After drying each painting and drying at room temperature (20 ℃) for 1 day)

(Iii) Antifouling paint: Antifouling paint compositions of Examples and Comparative Examples were coated on the above specimens to a thickness of 300 mu m, and then dried at room temperature (20 DEG C) for 1 week

Ⅳ Test conditions: The test was carried out for 18 months on a raft type raft mounted on the sea coast of Geoje Island (Ulsan, Korea) and in Ulsan, Korea.

V Evaluation criteria

5: In the absence of marine organisms (non-polluted)

4: A state in which a thin slime layer is observed

3: A thick slime layer is observed or the vegetable contamination area is less than 20% of the effective area of the specimen

2: The condition that the vegetable contamination area is 20 to 50% of the effective area of the specimen

1: The condition that the vegetable contamination area is 50 ~ 100% of the effective area of the specimen

X: Animal contamination occurred

Item Example 3 Example 4 Comparative Example 2 Solids 49.6% 49.7% 49.7% Viscosity 101KU 96KU 103KU Zhejiang Province 125KU 113KU Not measurable Antifouling performance 5 5 3

As shown in the results of Tables 2 and 4, the antifouling paint composition according to one embodiment of the present invention has excellent antifouling performance and storage stability while securing storage stability of the composition.

Claims (5)

Siloxane-urethane copolymers, and
A hydrolyzable functional group-containing oligomer or prepolymer containing at least one of a metal and a silyl group,
Wherein the siloxane-urethane copolymer has a chemical structure represented by the following formula (1):
[Chemical Formula 1]

Wherein R ₁ is H or CH ₃ , R ₂ is a C ₂ or more aliphatic group, alicyclic group or aromatic group, R ₃ is a direct bond or a C ₁ to C ₁₅ aliphatic group, an alicyclic group, R ₄ is a direct bond or a C ₁ to C ₁₅ aliphatic group and R ₅ is a direct bond or a (C _a H _2a O) _{b wherein} a = 1-4, b = 0-10 _, R ₆ to R ₁₀ are C ₁ to C ₈ aliphatic, alicyclic or aromatic groups, n is 0 to 5, and m is 5 to 200). delete The method according to claim 1,
Wherein the hydrolyzable functional group-containing oligomer or prepolymer comprises a repeating unit derived from the following formula (2) or (3).
(2)

(3)

Wherein R ₁₁ is H or CH ₃ and R ₁₂ is a C ₁ to C ₃₀ aliphatic, alicyclic or aromatic group, R ₁₃ is H or CH ₃ , and R ₁₄ to R ₁₆ are C ₁ to C ₂₀ aliphatic group, alicyclic group, or aromatic group, and Me is selected from the group consisting of Zn, Cu, Mo, and Co. The method according to claim 1,
Wherein the siloxane-urethane copolymer is 10 to 70 parts by weight based on solids, and the hydrolyzable functional group-containing oligomer or prepolymer is 10 to 90 parts by weight based on solids. A paint having an antifouling coating film formed on the surface thereof by using the composition for antifouling paint according to any one of claims 1 and 3 to 4.