KR102114058B1 - Additive for antifouling paint and antifouling paint composition comprising the same - Google Patents

Abstract

The present invention relates to an antifouling paint composition capable of forming a coating film having excellent abrasion resistance and crack resistance according to the additive for antifouling paint and the additive for antifouling paint.

Description

Antifouling paint additive and antifouling paint composition comprising the same {ADDITIVE FOR ANTIFOULING PAINT AND ANTIFOULING PAINT COMPOSITION COMPRISING THE SAME}

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

In general, when marine life is attached to the surface of the coating film coated on the ship, the frictional force between the surface of the coating film and the sea water increases when the ship is in operation, leading to a problem that consumption of fuel, which accounts for a large portion of the operating cost, increases. Accordingly, anti-fouling paints are applied to prevent adhesion of marine life and the like to the surface of the ship's coating film to reduce the friction between the surface of the coating film and the sea water during the operation of the ship.

Among the antifouling paints, SPC (Self Polishing Copolymer) type antifouling paints can be hydrolyzed with seawater, preventing marine organisms from adhering to the vessels due to the abrasion action of the coating film and elution of the antifouling agent during operation of the ship. Have a mechanism. The SPC type antifouling paint may be divided into a metal (Metal) containing antifouling paint and a silyl containing antifouling paint.

However, the silyl-containing antifouling coating tends to have a relatively low hydrolysis rate compared to an ion-bonding metal-containing antifouling coating, and thus has relatively low abrasion resistance. In addition, the metal-containing antifouling paint has a limited degree of abrasion due to the molecular weight of the binder resin or the glass transition temperature, etc., and is limited in application due to high viscosity of the final binder resin due to an increase in the hydrolysis machine.

Republic of Korea Patent Publication No. 2001-0038856

The present invention provides an additive for antifouling paint that can improve abrasion resistance and crack resistance of a coating film formed of an antifouling coating composition.

In addition, the present invention provides an antifouling paint composition comprising the additive for antifouling paint.

The present invention provides an additive for antifouling paint obtained by the reaction of a first organic acid to which one carboxyl group is bonded, a second organic acid to which 2 to 4 carboxyl groups are bonded, a metal compound, and an amine compound.

The present invention can provide an antifouling coating additive and an antifouling coating composition that can form a coating film having excellent appearance, antifouling property and crack resistance.

Hereinafter, the present invention will be described.

One. Antifouling  Additives for paints

The present invention provides an additive for antifouling paint obtained by reaction of a first organic acid with one carboxyl group bonded, a second organic acid with two to four carboxyl groups bonded, a metal compound and an amine compound.

The first organic acid to which the one carboxyl group is attached is Naphthenic Acid, Abietic acid, Benzoic acid, Stearic acid, Hydroxystearic acid (12-Hydroxystearic acid), It is selected from the group consisting of isononanoic acid, acetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, caproic acid and lauric acid. It may be one or more.

The 2 to 4 carboxyl group-coupled second organic acid is succinic acid, sebasic acid, succinic anhydride acid, glutaric acid, adipic acid , Azelaic Acid, Fumaric Acid, Diglycolic Acid, Citric Acid, Cyclohexanedicarboxylic Acid, Maleic Anhydride, Hexahydro Hexahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Tetrahydrophthalic anhydride Phosphatidic acid, Isophthalic acid, Terephthalic acid , Phthalic anhydride, naphthalic acid, diphenic acid, trimellitic anhydride, trimellitic acid, hemimellitic acid, trimesic acid (Trimesic Acid), 1,2,3,4-benzenetetracarboxylic acid, (1,2,3,4-Benzenetetracarboxylic Acid), Pyromellitic dianhydride, Mellitic acid, Tetrachlorophthalic anhydride, 5-butane-2ylbenzene-1,3-dicarboxylic acid (5-butan-2-ylbenzene-1,3-dicarboxylic acid), 5-sulfoisophthalate sodium salt (5-Sulfoisophthalic acid sodium salt) and 5-sulfoisophthalic acid lithium salt (5-S ulfoisophthalic acid lithium salt).

The metal compound may be an oxide in which a divalent metal is bonded, such as Cu, Mn, Co, or Zn, and may be, for example, kappa oxide (CuO) or zinc oxide (ZnO).

The amine-based compound controls the viscosity by blocking the ionic bond between the carboxyl group bound to the first organic acid or the second organic acid and the metal bound to the metal compound, and serves as a plasticizer.

The amine-based compound may be a compound represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₃ are the same as or different from each other, and each independently H or an alkyl group having 1 to 8 carbon atoms,

m and n are each independently an integer from 0 to 18.

A solvent may be added to the reaction between the first organic acid, the second organic acid, the metal compound, and the amine-based compound to accelerate the reaction or adjust the viscosity. As the solvent, xylene, toluene, deionized water, water, or pure water may be used.

The reaction between the first organic acid, the second organic acid, the metal compound, and the amine-based compound may be achieved through, for example, the following reaction formula.

[Scheme 1]

ZnO + H ₂ O = OH-Zn-OH

[Scheme 2]

OH-Zn-OH + R-COOH = COOH- [R-COO-Zn-COO-R] _n -COOH

[Scheme 3]

A plurality of COOH- [R-COO-Zn-COO-R] _n -COOH + amine compounds (eg alkylamine)

The reaction ratio of the first organic acid, the second organic acid, and the metal compound in the process of Scheme 2 may be a molar ratio of 1: 0.05 to 10: 0.05 to 10. When the reaction ratio is outside the above range, cake development, gelation, etc. may occur during the synthesis of the additive, and the appearance may become cloudy after synthesis.

The reaction ratio of the reactant of the first organic acid, the second organic acid and the metal compound and the amine compound in the process of Scheme 3 is 100: 0.1 to 20 weight ratio, or for example 100: 0.5 to 15 weight ratio, another example is 100: It may be 1 to 10 weight ratio. When the reaction ratio is outside the above range, plasticity may be low, resulting in cracking or difficulty in increasing the strength of the coating film.

The antifouling paint additive of the present invention as described above reacts a compound (a reactant of a first organic acid, a second organic acid and a metal compound) containing a hydrolysable metal-ester repeating unit with an amine compound that increases plasticity When it is used as an additive in an antifouling coating composition, it is possible to form a coating film having excellent appearance (improving surface roughness) and excellent antifouling property and crack resistance.

2. Antifouling  Paint composition

The antifouling coating composition of the present invention includes an antifouling resin and an additive for antifouling coating.

The antifouling resin contained in the antifouling coating composition of the present invention may be a commonly known SPC (Self Polishing Copolymer) type antifouling resin. The SPC type antifouling resin may be, for example, a compound represented by Formula 2 below.

[Formula 2]

In Chemical Formula 2,

R ₁ and R ₃ are the same or different from each other, and each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or an aliphatic hydrocarbon group containing an alicyclic, aromatic and double bond,

R ₂ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or an aliphatic hydrocarbon group containing an alicyclic, aromatic and double bond,

R ₄ is H, OH, CH ₂ OH, SO ₃ Na, SO ₃ Li, monovalent to tetravalent COOH, monovalent to tetravalent Cl,

M is Cu, Mn, Co, or Zn,

n is an integer from 1 to 50.

The content of the antifouling resin may be 10 to 60 parts by weight based on 100 parts by weight of the antifouling coating composition. When the content of the antifouling resin is less than 10 parts by weight, a coating film may be difficult to form or antifouling properties may be lowered, and when it exceeds 60 parts by weight, solid content (SVR: Solid VOLUME RATIO) is lowered due to an increase in viscosity, or workability or storage Stability may be degraded.

The antifouling paint additive included in the antifouling paint composition of the present invention is the above '1. Since it is the same as described in the section 'Additives for antifouling paints', a description thereof will be omitted.

The content of the additive for antifouling paint may be 0.5 to 20 parts by weight based on 100 parts by weight of the antifouling paint composition. When the content of the additive for antifouling paint is less than 0.5 part by weight, the antifouling property and crack resistance of the coating film may be lowered, and when it exceeds 20 parts by weight, the strength of the coating film may be lowered or over-abrasion of the antifouling coating film may occur. .

Meanwhile, the antifouling coating composition of the present invention may further include one or more additives selected from the group consisting of pigments, antifouling agents, flow inhibitors, anti-settling agents, plasticizers, antifoaming agents, and solvents.

The content of these additives may be 10 to 50 parts by weight based on 100 parts by weight of the antifouling coating composition when considering physical properties of the antifouling coating film.

Hereinafter, the present invention will be described in detail through examples.

However, the following examples are only to illustrate the present invention, the present invention is not limited by the following examples.

[ Example  1 to 5]

Each component was added to a tank, and the mixture was heated to about 100 ° C. while being slowly stirred to dissolve, and then kept at the elevated temperature for about 5 hours. Subsequently, the temperature was gradually raised to about 120 ° C. over 3 hours, and then cooled to about 95 ° C. and N ₂ was blown for about 10 minutes (5 cc / min) to prepare an additive for antifouling paint. At this time, the composition of each component is shown in Table 1 (content unit: g).

ingredient Furtherance Example 1 Example 2 Example 3 Example 4 Example 5 Second organic acid Succinic acid 42.6 - - - - Sebasic acid - 36.4 72.9 - -  hexahydrophthalic anhydride - - - 200 100 First organic acid Naphthenic acid - - 158.0 - - Abietic acid 216.9 326.2 - - 100 Lauric acid - - - 30 - Amine series
compound Dihexylamine - 9.3 9.3 - - Ditridecylamine 19.1 - - - 10 tributylamine - - - 15 - Metal compounds ZnO 58.3 58.3 58.3 58.3 58.3 solvent DIW 32.4 32.4 32.4 32.4 32.4 XYLENE 78.0 110.0 68 70.0 57.0 Properties Yield (g, Scale measurement) 447.3 572.6 398.9 405.7 357.7 Solid content (%, 150 ℃ * 30 min) 75.3 75.1 74.8 74.8 75.0 Amine Value (Auto-titrator) 6.3 4.9 7.1 11.2 4.1

[ Manufacturing example  1 to 6 and Comparative manufacturing example  1 to 2]

An antifouling coating composition having the composition of Table 2 was prepared by a conventional method.

Furtherance Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 compare
Preparation Example 1 compare
Preparation Example 2 Silyl-containing antifouling resin 226.9 226.9 226.9 200.2 226.9 226.9 251.9 231.9 Chlorinated Paraffin 34.6 34.6 34.6 34.6 34.6 34.6 34.6 34.6 Fe ₂ O ₃ 39.6 39.6 39.6 39.6 39.6 39.6 39.6 39.6 TALC 61.7 61.7 61.7 61.7 61.7 61.7 61.7 61.7 Cu ₂ O 495.5 495.5 495.5 495.5 495.5 495.5 495.5 495.5 Cu-PT 37.7 37.7 37.7 37.7 37.7 37.7 37.7 37.7 Rosin - - - - - - - 20.0 Additive of Example 1 26.7 - - - - - - - Additive of Example 2 - 26.7 - - - - - - Additive of Example 3 - - 26.7 53.4 - - - - Additive of Example 4 - - - - 26.7 - Additive of Example 5 - - - - - 26.7 Polylamide Wax 33.7 33.7 33.7 33.7 33.7 33.7 33.7 33.7 Xylene 43.6 43.6 43.6 43.6 43.6 43.6 45.3 45.3 TOTAL
(Unit: g) 1000.0 1000.0 1000.0 1000.0 1000.0 1000.0 1000.0 1000.0

[Experimental Example]

After forming a coating film with an antifouling coating composition prepared in each of the above Production Examples and Comparative Production Examples, the properties of the formed coating films were evaluated as follows, and the results are shown in Table 3 below.

1. Coating film abrasion rate (%): Balancing TEST (operating rate 70%, averaged for 3 months) was conducted, and the thickness of the reduced coating film compared to the initial coating film thickness was measured and expressed as a ratio.

1) Specimen: 10 × 150 (mm) non-ferrous metal

2) Antifouling coating composition: 100 µm coating, then dried for 1 week at room temperature (20 ℃)

3) Test conditions: Flight rate 70%, ship speed 5knots, 3 months

4) Evaluation criteria: Coating film thickness reduction rate ((Initial DFT-3 months later DFT) / Initial DFT * 100)

2, Rapid crack resistance: 60 ° C * 12 hours seawater deposition + -20 ° C frozen * 12 hours as 1 cycle to measure the number of cycles until no change occurs in the coating film

1) Specimen: 100 × 300 × 1.5 (㎜) steel plate

2) Specimen treatment: Sand blasting → Epoxy-based paint 150 μm → Epoxy binder paint 100 μm (after coating each paint, dried at room temperature (20 ° C.) for 1 day)

3) Anti-fouling coating composition: 600 µm coating and dried at room temperature (20 ℃) for 1 week

4) Test condition: 60 ℃ * 12 hours seawater deposition → -20 ℃ frozen * 12 hours left

5) Evaluation criteria: The higher the number of cycles, the better the crack resistance.

Properties Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 compare
Preparation Example 1 compare
Preparation Example 2 Coating wear rate
(%, Coating film thickness reduction rate) 14.3% 15.4% 13.1% 19.9% 14.7% 13.0% 10.5% 12.2% Crack resistance
(Cycle number) 17 16 16 15 16 18 15 12

Referring to Table 3, it can be seen that the coating film formed of the antifouling coating composition to which the additive for antifouling roads of the present invention is applied is smoothly hydrolyzed and has a high wear resistance and high crack resistance.

Claims (5)

An additive for antifouling paint obtained by reaction of a first organic acid with one carboxyl group bonded, a second organic acid with two to four carboxyl groups bonded, a metal compound and an amine compound.
The method according to claim 1,
The metal compound is Cu, Mn, Co and Zn is an oxide containing one or more selected from the group consisting of an additive for antifouling paint.
The method according to claim 1,
The amine-based compound is an additive for antifouling paints, which are compounds represented by Formula 1 below.
[Formula 1]

In Chemical Formula 1,
R ₁ to R ₃ are the same as or different from each other, and each independently H or an alkyl group having 1 to 8 carbon atoms,
m and n are each independently an integer from 0 to 18.
The method according to claim 1,
The first organic acid, the second organic acid and the metal compound has a reaction ratio of 1: 0.05 to 10: 0.05 to 10 molar ratio of the additive for antifouling paint.
Antifouling resin and
An antifouling coating composition comprising the additive for antifouling coating according to any one of claims 1 to 4.