KR101970431B1 - Antifouling resin and antifouling paint composition comprising the same - Google Patents

Abstract

The present invention relates to an anti-fouling resin and an anti-fouling paint composition including the same. The anti-fouling resin of the present invention comprises: an acrylic resin obtained by a reaction of at least one of a monomer including a double bond and an alkyl group and a monomer including a double bond and a silyl group, with a monomer including a double bond and a carboxyl group; a metal compound; and a silicone-modified organic acid.

Description

TECHNICAL FIELD [0001] The present invention relates to an antifouling resin composition and an antifouling paint composition containing the antifouling resin composition.

The present invention relates to an antifouling resin and an antifouling paint composition comprising the antifouling resin.

In general, when marine life is attached to the surface of a coated paint on a ship, frictional force between the surface of the coating and sea water increases during operation of the vessel, and the increase in the weight of the vessel increases the consumption of fuel costs, which is a large part of the operation expenses. Accordingly, an antifouling coating is applied to prevent the adhesion of marine life and the like to the surface of the coating film of the ship, thereby reducing the frictional force between the surface of the coating film and the sea water during navigation of the ship.

The antifouling paint is an antifouling paint that exhibits antifouling performance by eluting an antifouling agent such as copper oxide as the antifouling resin is hydrolyzed in the film, and an antifouling paint exhibiting antifouling performance by lowering the surface tension of the coating film so that marine life is not attached to the hull Can be divided. Among these, the Foul-Release type, which exhibits antifouling performance by lowering the surface tension of the coating film, is environmentally friendly and has the advantage of exhibiting its effect semi-permanently, There is a disadvantage in that it is difficult to recover the contaminated parts once again.

To overcome this problem, a technique has been proposed in which an antifouling performance of a coating film is enhanced by applying a fluorine-denatured additive (see Patent Document 1 below). However, this technique still has the disadvantage that the coated film contaminated by the long stagnation period or the low speed operation is not restored.

In addition, a technology has been proposed in which a monomer having a silicon group and having hydrolyzable silyl or metal groups is introduced to enable regeneration of the contaminated coating film, thereby improving the antifouling performance of the coating film See Patent Document 2 below). However, this technique has a disadvantage in that the appearance of the antifouling resin is clogged due to the collision between the hydrophilic monomer and the hydrophobic silicone acrylic monomer, and the synthetic stability such as the generation of the tie during the synthesis is poor.

Patent Document 1: International Publication No. WO2007-102741 Patent Document 2: International Publication No. WO2011-046087

The present invention provides an antifouling resin having excellent synthetic stability.

The present invention also provides an antifouling paint composition comprising the antifouling resin and capable of forming a coating film having low frictional resistance, excellent antifouling property, crack resistance, discoloration resistance, and the like.

The present invention relates to an acrylic resin, a metal compound and a silicone-modified organic acid obtained by a reaction between a monomer containing a double bond and an alkyl group, a monomer containing a double bond and a silyl group, and a monomer containing a double bond and a carboxyl group, To provide an antifouling resin.

The monomer comprising the double bond and the alkyl group is selected from the group consisting of C ₃ to C ₂₄ alkyl vinyl ethers, C ₅ to C ₂₄ cycloalkyl vinyl ethers, C ₂ to C ₂₄ alkyl (meth) acrylates, and C ₅ to C ₂₄ Cycloalkyl (meth) acrylate, and the like.

The monomer containing the double bond and the silyl group may be a C ₃ to C ₄₀ silyl (meth) acrylate.

The monomer containing a double bond and a carboxyl group may be a monomer obtained by a ring-opening reaction of meth (acrylic acid) or a monomer containing a double bond and an alcohol group and an acid anhydride monomer.

The reaction ratio of the monomer containing at least one of the double bond and the alkyl group and the monomer containing the double bond and the silyl group and the monomer containing the double bond and the carboxyl group may be in a weight ratio of 50 to 95: have.

The metal bonded to the metal compound may be at least one selected from the group consisting of Zn, Cu, Mg, Ca, Fe, Mn, and Co.

The silicone-modified organic acid may be a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R _1, R ₃ and R ₄ are each independently selected from the group consisting of C ₀ to C ₁₅ aliphatic hydrocarbon groups, C ₃ to C ₁₅ alicyclic hydrocarbon groups and C ₆ to C ₁₅ aromatic hydrocarbon groups, and R ₂ And R ₅ are each independently - (C _a H _2a O) _b- (a = an integer from 0 to 4, b = an integer from 0 to 10), R ₆ is hydrogen or a C ₁ to C ₅ alkyl group, n is an integer of 5 to 200;

The silicone-modified organic acid may be an organic acid obtained by a ring-opening reaction of mono-alcohol-modified polysiloxane and anhydrous acid, and the monoalcohol may be carbitol.

The acid compound may be selected from the group consisting of acetic acid, formic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, succinic acid, malonic acid, oxanic acid, glutaric acid, adipic acid, , At least one low molecular weight organic acid selected from the group consisting of fumaric acid, iglycolic acid, citric acid, phthalic acid, isophthalic acid, naphthenic acid and terephthalic acid.

The low-molecular organic acid may be a half ester obtained by reaction of an acid anhydride with an alcohol.

The reaction ratio of the acrylic resin, the metal compound and the acid compound may be a molar ratio of 0.75 to 1.05: 1: 0.75 to 1.25.

On the other hand, the present invention provides an antifouling paint composition comprising the antifouling resin.

The present invention provides an antifouling paint and antifouling paint composition which is capable of forming a coating film having excellent antifouling property, crack resistance, discoloration resistance, and low friction resistance even though the antifouling agent is used in a small amount or not at all .

Hereinafter, the present invention will be described.

One. Antifouling  Suzy

The antifouling resin of the present invention can be obtained by the reaction of an acid compound including an acrylic resin, a metal compound and a silicone-modified organic acid.

<Acrylic resin>

The acrylic resin may be obtained by reacting at least one monomer selected from the group consisting of a monomer having a double bond and an alkyl group, a monomer having a double bond and a silyl group, and a monomer having a double bond and a carboxyl group.

The monomer containing the double bond and the alkyl group controls the glass transition temperature (T _g ) and hydrophilicity of the antifouling resin. These monomers containing a double bond and an alkyl group include C ₃ to C ₂₄ alkyl vinyl ethers, C ₅ to C ₂₄ cycloalkyl vinyl ethers, C ₂ to C ₂₄ alkyl (meth) acrylates, and C ₅ to C ₂₄ (Meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylate, isobornyl (meth) acrylate, 2-methoxyethyl acrylate, dodecylvinyl (meth) acrylate, Ether, octadecyl vinyl ether, and 2-ethylhexyl vinyl ether.

The monomer containing the double bond and the silyl group is hydrolyzed in seawater to cause the coating film to be worn. The monomers comprising such double bonds and silyl groups may be C ₃ to C ₄₀ silyl (meth) acrylates and include, for example, trimethylsilyl (meth) acrylate, tributylsilyl (meth) acrylate, triisopropylsilyl (Meth) acrylate, and dibutylmethylsilyl (meth) acrylate.

The monomer containing a double bond and a carboxyl group reacts with the metal compound during the production of the antifouling resin, and hydrolysis of the coating film occurs in the seawater due to the functional group derived therefrom. Such a monomer containing a double bond and a carboxyl group may be a monomer obtained by ring-opening reaction of (meth) acrylic acid or a monomer containing a double bond and an alcohol group and an acid anhydride monomer.

The monomer containing the double bond and the alcohol group may be a C ₂ to C ₁₂ hydroxyalkyl (meth) acrylate, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) (Meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxybutyl have.

The acid anhydride monomers may be C ₁ to C ₂₄ aliphatic acid anhydride monomers, alicyclic acid anhydride monomers, or aromatic acid anhydride monomers, for example, succinic anhydride, maleic anhydride, dodecyl succinic anhydride, octyl succinic anhydride, (PMDA), 3,3 ', 4,4-oxydiphthalic acid dianhydride (ODPA), and the like can be used as the anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, pyromellitic dianhydride , 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA), 4,4'-diphthalic acid (hexafluoroisopropylidene) anhydride (6FDA), benzoquinonetetracarboxylic dianhydride, Ethylene tetracarboxylic acid dianhydride and (meth) acrylic acid anhydride.

The reaction ratio of the monomer containing at least one of the double bond and the alkyl group and the monomer containing the double bond and the silyl group and the monomer containing the double bond and the carboxyl group is preferably from 50 to 95: By weight. When the reaction rate is out of the above range, the antifouling property and crack resistance of the coating film may be lowered.

Such an acrylic resin can be usually obtained by a known radical polymerization reaction. The acrylic resin thus obtained may have an acid value (based on solid content) of 50 to 350 mgKOH / g. When the acid value of the acrylic resin is less than 50 mgKOH / g, the abrasion rate, antifouling property and discoloration resistance of the coating film may be deteriorated. When the acid value is more than 350 mgKOH / g, the crack resistance of the coating film is lowered, Can be increased.

<Metal compound>

The metal compound reacts with the carboxyl group of the organic acid contained in the acrylic resin and the acid compound, and the metal ion derived therefrom can induce wear of the coating film in the seawater. The metal compound may be a compound in which at least one divalent metal selected from the group consisting of Zn, Cu, Mg, Ca, Fe, Mn and Co is bonded, and may be, for example, zinc oxide (ZnO).

<Acid compound>

The acid compound includes a silicon-modified organic acid. The silicone-modified organic acid reacts with the metal compound during the production of the antifouling resin. The functional group derived therefrom can hydrolyze the coating film in the seawater, lower the frictional resistance, It is possible to improve the property.

The silicone-modified organic acid may be an organic acid containing a polysiloxane structure and a carboxyl group, and the silicone-modified organic acid may be used in an amount of 10 to 100 parts by weight based on the total weight of the acid compound. When the amount of the organic acid containing the polysiloxane structure and the carboxyl group is less than 10 parts by weight, it may be difficult to lower the frictional resistance.

The silicone-modified organic acid may be an organic acid obtained by a ring-opening reaction of a monoalcohol-modified polysiloxane and an anhydride, and the monoalcohol may be a carbitol. The silicone-modified organic acid may be a compound represented by Formula 1 below.

[Chemical Formula 1]

In Formula 1,

R _1, R ₃ and R ₄ are each independently selected from the group consisting of C ₀ to C ₁₅ aliphatic, hydrocarbon groups, C ₃ to C ₁₅ alicyclic hydrocarbon groups and C ₆ to C ₁₅ aromatic hydrocarbon groups, R ₂ and R ₅ are each independently (C _a H _2a O) _b (a = an integer of 0 to 4, b = an integer of 0 to 10), R ₆ is hydrogen or a C ₁ to C ₅ alkyl group, n Is an integer of 5 to 200. [ In formula (1), R _1, R ₃ and R ₄ are each independently a C ₁ to C ₁₅ alkyl group, and R ₂ and R ₅ are each independently (C _a H _2a O) _b (a = 0, b = 0), and R &lt; ₆ &gt; may be hydrogen or a methyl group.

The acid compound may further include a low molecular weight organic acid having a molecular weight of 500 or less. The low molecular weight organic acid may be at least one selected from the group consisting of C ₁ to C ₂₄ aliphatic acids, alicyclic acids and aromatic acids, including organic acids having monofunctional, bifunctional or trifunctional or higher functional groups. The low molecular weight organic acid may be, for example, acetic acid, formic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, succinic acid, malonic acid, oxanic acid, glutaric acid, adipic acid, Citric acid, phthalic acid, isophthalic acid, terephthalic acid, and naphthenic acid. [0033] The term &quot; acidic &quot;

The low molecular weight organic acid may also be a half ester obtained by the reaction of an acid anhydride with an alcohol.

The acid anhydride may be at least one member selected from the group consisting of C ₁ to C ₂₄ aliphatic acid anhydrides, alicyclic acid anhydrides and aromatic acid anhydrides, and examples thereof include succinic anhydride, maleic anhydride, dodecylsuccinic anhydride, (PMDA), 3,3 ', 4,4-oxydiphthalic acid anhydride (e.g., trimethylphthalic anhydride), phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, ODPA), 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA), 4,4'-diphthalic acid (hexafluoroisopropylidene) anhydride (6FDA), benzoquinone tetracarboxylic acid Anhydride, ethylene tetracarboxylic acid dianhydride, and (meth) acrylic acid anhydride.

The alcohols may be monofunctional, bifunctional or trifunctional polyhydric alcohols (C ₁ to C ₁₂ aliphatic alcohols, alicyclic alcohols, aromatic alcohols), for example, ethylene glycol, propylene glycol, trimethylolpropane, trimethyl Diethylene glycol, diethylene glycol, triethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, ditrimethylolpropane, Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyisopropyl (meth) acrylate, butanediol mono (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and caprolactone (meth) acrylate.

The antifouling resin of the present invention is obtained by the condensation reaction of the acrylic resin, the metal compound and the acid compound, wherein the reaction ratio may be a molar ratio of 0.75 to 1.05: 1: 0.75 to 1.25. The condensation reaction may be carried out in a conventional manner in the presence of a solvent (for example, xylene, toluene, deionized water, etc.).

As described above, the antifouling resin of the present invention obtained by using an acid compound containing a silicon-modified organic acid together with an acrylic resin and a metal compound efficiently hydrolyzes in seawater and lowers the surface tension of the coating film to lower the frictional resistance And the discoloration resistance and crack resistance of the coating film can be enhanced.

2. Antifouling  Paint composition

The present invention provides an antifouling paint composition comprising the above-mentioned antifouling resin. Such an antifouling paint composition of the present invention can form a coating film having excellent discoloration resistance, crack resistance, antifouling property and low friction resistance by including the above-mentioned antifouling resin.

The content of the antifouling resin may be 20 to 100 parts by weight based on the total weight of the antifouling paint composition (based on the solid content). When the content of the antifouling resin is less than 20 parts by weight, crack resistance and antifouling property of the coating film .

Meanwhile, the antifouling paint composition of the present invention can be used as an antifouling paint (usually known as SPC antifouling resin), auxiliary resin, pigment, film elution regulator, antifouling agent, anti-sagging agent, And at least one selected from the group consisting of

The coating film elution controlling agent controls the dissolution rate of the coating film against the controlled abrasion behavior of the coating film in seawater. As such a coating film elution regulator, at least one selected from the group consisting of rosin, rosin derivatives, monocarboxylic acids, and salts thereof may be used. Examples of the rosin include rosin rosin, wood rosin, tall oil rosin, and the like. Examples of the rosin derivatives include disodium rosin (low melting point), hydrogenated rosin, polymerized rosin, metal salts (copper salt, zinc salt or magnesium salt) of rosin and rosin derivatives, and rosin amine. The monocarboxylic acid may be, for example, a C ₅ to C ₃₀ fatty acid, a synthetic fatty acid, or a naphthenic acid.

The content of the coating film elution regulating agent may be determined depending on the antifouling property and water resistance of the coating film, and may be 0.1 to 25 parts by weight based on the total weight of the antifouling paint composition (based on the solid content).

As the antifouling agent, conventionally known organic compounds or inorganic compounds can be used.

The pigment may be zinc oxide, titanium white, iron oxide red, or talc for improving the strength of the coating film, controlling the wear rate, and coloring.

As the plasticizer, chlorinated paraffin or the like which contributes to improving the crack resistance of the coating film can be used.

As the auxiliary resin, an acrylic resin or a polyalkyl vinyl ether (vinyl ether (co) polymer) may be used.

Examples of the solvent include an aliphatic solvent, an aromatic solvent (for example, xylene, toluene, etc.), a ketone solvent, an ester solvent, or an ether solvent.

In addition, the antifouling paint composition of the present invention may further include additives conventionally known in the field of antifouling paints.

Hereinafter, the present invention will be described in detail with reference to examples.

However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Synthetic example  One]

A thermometer and a condenser was charged with 540 g of xylene and 720 g of butanol in a nitrogen atmosphere and the temperature was raised to the reflux temperature (about 120 ° C). A mixture of 360 g of methacrylic acid, 360 g of methyl methacrylate, 900 g of ethyl acrylate, 180 g of 2-methoxyethyl acrylate, 540 g of xylene and 18 g of azobis-methylbutyronitrile was added dropwise uniformly for 4 hours The mixture was then refluxed for 2 hours and cooled. As a result, a colorless acrylic resin having a solid content of 50.2% by weight was produced.

[ Synthetic example  2]

A thermometer and a condenser was charged with 540 g of xylene and 720 g of butanol in a nitrogen atmosphere and the temperature was raised to the reflux temperature (about 120 ° C). A mixture of 360 g of methacrylic acid, 360 g of methyl methacrylate, 720 g of ethyl acrylate, 180 g of tri-isopropylsilyl acrylate and 180 g of 2-methoxyethyl acrylate, 540 g of xylene, and 54 g of azobis-methylbutyronitrile Was added dropwise uniformly for 4 hours, then refluxed for 2 hours and cooled. As a result, a colorless acrylic resin having a solid content of 50.2% by weight was produced. At this time, the amount of each component used is shown in Table 1 below.

Part Raw material Synthetic example  One Synthetic example  2 One Xylene 540.0 g 540.0 g n-butanol 720.0 g 720.0 g 2 Methacrylic acid 360.0 g 360.0 g Methyl methacrylate 360.0 g 360.0 g Ethyl acrylate 900.0 g 720.0 g Tri-isopropylsilyl acrylate - 180.0 g 2-methoxyethyl acrylate 180.0 g 180.0 g 3 Xylene 540.0 g 540.0 g Azobis-methylbutyronitrile 18.0 g 54.0 g

[ Example  One]

A thermometer and a condenser, 361.8 g of the acrylic resin of Synthesis Example 1, 34.1 g of zinc oxide (ZnO), 607.0 g of Carboxylic acid modified silicone fluid (Sinetsu, X-22-3710), 612.0 g of xylene, 3.8 g of deionized water was added and condensation reaction was carried out in a nitrogen atmosphere, followed by cooling down to 70 캜 to obtain a colorless antifouling resin having a solid content of 50.4% by weight.

[ Example  2]

A flask equipped with a stirrer, a thermometer and a condenser was charged with 651.2 g of the acrylic resin of Synthesis Example 1, 61.3 g of zinc oxide (ZnO), 546.3 g of Carboxylic acid modified silicone fluid (Sinetsu, X-22-3710), naphthenic acid ), 648.0 g of xylene, and 6.8 g of deionized water. The mixture was condensed under a nitrogen atmosphere, and then cooled to 70 캜 to obtain a brown antifouling resin having a solid content of 50.3% by weight.

[ Example  3]

A thermometer and a condenser, 361.8 g of the acrylic resin of Synthesis Example 2, 34.1 g of zinc oxide (ZnO), 607.0 g of Carboxylic acid modified silicone fluid (Sinetsu, X-22-3710), 612.0 g of xylene, 3.8 g of deionized water was added and condensation reaction was carried out in a nitrogen atmosphere, followed by cooling down to 70 캜 to obtain a colorless antifouling resin having a solid content of 50.4% by weight.

[ Comparative Example  One]

904.5 g of the acrylic resin of Synthesis Example 1, 85.2 g of zinc oxide (ZnO), 231.3 g of naphthenic acid, 270.0 g of xylene and 9.4 g of deionized water were placed in a four-necked flask equipped with a thermometer and a condenser, Followed by cooling down to 70 캜 to obtain a brown stainproof resin having a solid content of 50.1% by weight.

[ Manufacturing example  1, 2, and Comparative Manufacturing Example  1, 2]

An antifouling paint composition having the composition shown in the following Table 2 was prepared by a conventional method.

ingredient Production Example 1 Production Example 2 Production Example 3 Comparative Preparation Example 1 Comparative Production Example 2 The antifouling resin of Example 1 60.0 - - - The antifouling resin of Example 2 - 30.0 - - The antifouling resin of Example 3 60 The antifouling resin of Comparative Example 1 - - 30.0 30.0 Tridecylamine
(tridecyl amine, TDA) 1.0 3.0 1.0 3.0 3.0 Iron oxide
(iron oxide Red 308) 5.0 5.0 5.0 5.0 5.0 Talc (NA-400) 5.0 7.0 5.0 12.0 5.0 ZnO 10.0 15.0 10.0 16.0 5.0 Xylene 16.0 31.0 16.0 31.0 16.0 Copper oxide (Cu ₂ O) - 5.0 - - 30.0 Copper pyricion
(copper pyrithione) - 1.0 - - 3.0 Amide wax
(Amide wax, Monoral 5500) 3.0 3.0 3.0 3.0 3.0 Sum 100 100 100 100 100

[Experimental Example]

The following properties were evaluated using the antifouling paint compositions prepared in Production Examples and Comparative Production Examples, and the results are shown in Table 3 below.

- Solids

1) Test conditions: Antifouling paint composition About 3.0 g sampling, 150 占 폚 占 24 hours

2) Solid content (wt.%) = Weight after heat drying / Sample weight × 100 (%)

- Viscosity: 25 캜, KU Viscometer

- discoloration resistance

1) Specimen: 150 x 70 x 3 (mm) Glass Specimen

2) Specimen treatment: xylene washing and drying

3) Painting: Drying at room temperature (20 ° C) for one week after coating at 250 μm

4) Test conditions: After immersing in fresh water container, after removing a certain amount of fresh water at intervals of 1 day, observed discoloration degree, visual determination - 14 days observation

5) Evaluation criteria: 5 (good) -1 (bad)

- Crack resistance

1) Specimen: 100 x 300 x 1.5 (mm)

2) Specimen treatment: Sand blasting → Epoxy system paint 150 ㎛ → Epoxy binder paint 100 ㎛ (After drying each painting and drying at room temperature (20 ℃) for 1 day)

3) Coating: Drying at room temperature (20 캜) for one week after coating at 600 탆

4) Test conditions: 23 ℃ sea water 24 hours immersion → 24 hours outdoor drying - 30 times repeated

5) Evaluation Criteria

5: No cracks or visible defects

4: Less than 5% of the total area of test specimen.

3: 5-20% cracks in the total area of test specimen

2: 20-50% cracks in the total area of test specimen

1: 50-70% cracks in the total area of test specimen

 0: More than 70% of the total area of the specimen is cracked.

- Friction resistance

1) Specimen: 50 mm in diameter x 100 mm in height The antifouling paint composition was applied to a stainless steel cylinder and dried at room temperature (20 ° C) for 7 days.

2) Test conditions: After rotating the specimen at 1,000 rpm for 3 days in seawater, measure the frictional resistance by torque meter (Torque: Ncm)

- Antifouling

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

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

3) Painting: Drying at room temperature (20 ° C) for one week after coating at 300 μm

4) Test conditions: 1 m below the sea level in a raft type test equipment installed on the coast of Ulsan (east coast) and Geoje Island (south coast)

5) 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 20-50% 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

Properties Manufacturing example  One Manufacturing example  2 Manufacturing example  3 Comparative Manufacturing Example  One Comparative Manufacturing Example  2 Solids (NV.) 51.7% 51.5% 51.7% 51.5% 51.5% Viscosity (Vis.) 85 KU 95KU 90 KU 100KU 105KU My discoloration property 5 5 5 5 3 Crack resistance 5 5 5 3 3 Frictional resistance 8.7 9.8 8.2 13.5 12.8 Antifouling 5 5 5 One 4

Referring to Table 3, it can be confirmed that the coating film formed from the antifouling paint composition of the present invention has excellent discoloration resistance, crack resistance, antifouling property and low frictional resistance.

Claims (12)

An acrylic resin obtained by a reaction of a monomer containing a double bond and an alkyl group and a monomer containing a double bond and a silyl group and a monomer containing a double bond and a carboxyl group,
Metal compounds and
An antifouling resin obtained by the reaction of an acid compound containing a silicone-modified organic acid. The method according to claim 1,
Wherein the monomer comprising the double bond and the alkyl group is selected from the group consisting of C ₃ to C ₂₄ alkyl vinyl ethers, C ₅ to C ₂₄ cycloalkyl vinyl ethers, C ₂ to C ₂₄ alkyl (meth) acrylates, and C ₅ to C ₂₄ (Meth) acrylate, and at least one selected from the group consisting of cycloalkyl (meth) acrylate. The method according to claim 1,
Wherein the monomer containing the double bond and the silyl group is a C ₃ to C ₄₀ silyl (meth) acrylate. The method according to claim 1,
Wherein the monomer containing a double bond and a carboxyl group is a meth (acrylic acid), or a monomer obtained by a ring-opening reaction of a monomer containing a double bond and an alcohol group and an acid anhydride monomer. [3] The method according to claim 1, wherein the reaction ratio of the monomer containing at least one of the double bond and the alkyl group, and the monomer containing the double bond and the silyl group, and the monomer containing the double bond and the carboxyl group is from 50 to 95: 50 &lt; / RTI &gt; by weight. The method according to claim 1,
Wherein the metal bonded to the metal compound is at least one selected from the group consisting of Zn, Cu, Mg, Ca, Ba, Fe, Mn and Co. The method according to claim 1,
Wherein said silicone-modified organic acid is a compound represented by the following formula (1).
[Chemical Formula 1]

In Formula 1,
R _1, R ₃ and R ₄ are each independently selected from the group consisting of C ₀ to C ₁₅ aliphatic hydrocarbon groups, C ₃ to C ₁₅ alicyclic hydrocarbon groups and C ₆ to C ₁₅ aromatic hydrocarbon groups,
R ₂ and R ₅ are each independently (C _a H _2a O) _b (a = an integer of 0 to 4, b = an integer of 0 to 10)
R ₆ is hydrogen or a C ₁ to C ₅ alkyl group,
n is an integer of 5 to 200; The method according to claim 1,
Wherein the silicone-modified organic acid is an organic acid obtained by a ring-opening reaction between a monoalcohol-modified polysiloxane and an anhydride. The method according to claim 1,
The acid compound may be selected from the group consisting of acetic acid, formic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, succinic acid, malonic acid, oxanic acid, glutaric acid, adipic acid, , At least one low molecular weight organic acid selected from the group consisting of fumaric acid, iglycolic acid, citric acid, phthalic acid, isophthalic acid, naphthenic acid and terephthalic acid. The method of claim 9,
Wherein the low molecular weight organic acid is a half ester obtained by the reaction of an acid anhydride with an alcohol and has a molecular weight of 500 or less. The method according to claim 1,
Wherein the reaction ratio of the acrylic resin, the metal compound, and the acid compound is a molar ratio of 0.75 to 1.05: 1: 0.75 to 1.25. An antifouling paint composition comprising an antifouling resin according to any one of claims 1 to 11.