KR101267282B1 - Antifouling coating composition with excellent antifouling property by the various molecular weight distribution control - Google Patents

Abstract

The present invention provides an antifouling coating composition comprising a binder resin, a metal oxide, and an organic antifouling agent, wherein the binder resin (A) has a branched structure in which a hydroxyl group of a polyhydric alcohol terminal is combined with at least one selected from fatty acids and acid anhydrides. An ester compound having a carboxyl group; (B) transition metal-containing ester compounds; (C) a transition metal compound containing an unsaturated double bond; And (D) a radically polymerized monomer comprising an unsaturated double bond is obtained by copolymerization. According to the present invention, the flexibility and material adhesion of the coating film is improved, the hardness of the coating film is improved by controlling the molecular weight of the ester compound, and the antifouling performance can be induced by increasing the hydrolysis rate, and the molecular weight and amount and type of polar groups By introducing a synthetic technology that can control the appropriately more diverse antifouling paint can be designed.

Description

Antifouling coating composition with excellent antifouling property by the various molecular weight distribution control

The present invention relates to an antifouling coating composition having excellent long-term antifouling properties through various molecular weight distribution adjustments, and more particularly to a copper-free type antifouling coating composition having excellent long-term antifouling properties through various molecular weight distribution adjustments.

When the bottom, underwater structure, and fishing nets are exposed to water for a long time, their appearance will be damaged if they adhere to and propagate various aquatic organisms such as oysters, mussels, barnacles, plants such as seaweed (Haitai), or bacteria. In some cases, the function may be impaired.

In particular, when such aquatic organisms adhere to and propagate on the bottom, surface roughness of the entire vessel may increase, resulting in lowering of ship speed and expansion of fuel economy. In addition, in order to remove such aquatic life from the bottom, a huge labor and work time is required.

In addition, bacteria adhere to and propagate in underwater structures, and in addition, slime (sludge material) is attached thereto to cause decay, or large adherents adhere to the surface of underwater structures such as steel structures. When breeding and damaging the corrosion prevention coating film etc. of the underwater structure, there exists a possibility that damage may occur, such as the strength and the function of the underwater structure fall, and the life-span will fall remarkably. In order to prevent such damage, various antifouling paints are applied to the bottom and the like, and various antifouling paints have been proposed.

Conventionally, the form of adding a tin compound as the antifouling paint for solving the above problems has been most used. Such antifouling paints are inexpensive, easy to handle, and have excellent antifouling performance. However, tin compounds are known to be a major cause of marine pollution that releases environmental hormones, and their use is limited.

Recently, it is a self-wearing antifouling paint that exhibits antifouling performance by using the principle that the antifouling paint film is gradually worn out when the vessel is sailed, instead of having no tin compound. The self-wear antifouling paint does not emit environmental hormones, but the strength of the coating is weak, so the paint should be frequently applied, and the coating itself is poor in antifouling performance. have.

Korean Patent Laid-Open Publication No. 1999-61474 discloses an antifouling agent comprising a self-wearing binder having a half ester or a half amide at a polymer side chain end as a colorant and a metal-containing antifouling agent. Start paint. In addition, Korean Patent No. 254651 discloses an antifouling paint made of a vinyl resin made of a vinyl polymer having a plurality of sheep base-type primary amino groups in a molecule thereof. However, the antifouling paints disclosed in the patent have a problem that the antifouling component is eluted into the seawater by reaction with seawater. As a result, the durability of the coating film is poor, and frequent repair painting is required, and when the anchoring component is not actively eluted, a large amount of foreign matter is attached. In addition, this type of antifouling paint has a disadvantage in that it is undesirable from an environmental point of view due to the outflow of seawater of the antifouling component.

Japanese Patent Laid-Open No. 2000-510891 discloses a marine antifouling paint containing a rosin, a fiber, and a polymer flexibility-imparting agent component and discloses excellent weather resistance. Moreover, poly (meth) acrylate, polyester resin, etc. are mentioned as an example as a polymer flexibility giving agent component. However, as the binder resin, a rosin metal salt, which is one kind of a self-wearing polymer, is used.

Korean Unexamined Patent Publication No. 2009-63736 discloses an antifouling paint including a prepolymer solution and a silicone resin, a fluorinated resin, and an antimicrobial agent. Although antifouling coating compositions are disclosed that can reduce the frictional resistance of the surface and maintain excellent durability such as crack resistance and abrasion resistance, there is a problem in that the wear rate of the antifouling paint cannot be easily controlled.

In order to solve the above problems, by controlling the carboxyl group at the end of the binder as a polyhydric alcohol, various molecular weight distribution is controlled to provide an antifouling coating composition capable of controlling antifouling performance, wear rate and coating performance. do.

In addition, another object of the present invention is to provide a method for producing an antifouling coating composition capable of manufacturing a coating in a more various form that can control the antifouling performance, wear rate and coating performance by adjusting the various molecular weight distribution.

In order to achieve the above object,

In the antifouling coating composition comprising a binder resin, a metal oxide, and an organic antifouling agent, the binder resin is

(A) an ester compound containing a carboxyl group represented by formula (1) having a branched structure in which a hydroxyl group of a polyhydric alcohol terminal is bonded with at least one selected from fatty acids and acid anhydrides;

임),(here,

being),

(B) a transition metal-containing ester compound represented by the following formula (2);

(C) a transition metal compound containing an unsaturated double bond; And

(D) An antifouling coating composition characterized by being obtained by copolymerizing a radically polymerized monomer containing an unsaturated double bond,

X is an alkyl group or cycloalkyl group having 2 to 15 carbon atoms, Y is an alkylene or polyalkyl ether group having 2 to 8 carbon atoms, Z is an alkyl group having 2 to 12 carbon atoms, m, n is an integer of 1 to 8 ,

M is a metal element, R ₄ provides an antifouling coating composition is a monobasic organic acid.

To achieve these and other objects,

In the method for producing an antifouling coating composition comprising a binder resin, a metal oxide, and an organic antifouling agent, the binder resin is

(i) synthesizing a carboxylic acid-containing ester compound represented by Formula 1 obtained by condensation of a saturated acid containing a carboxyl group with a polyhydric alcohol having 2 to 10 carbon atoms or an acid anhydride and the polyhydric alcohol;

[Formula 1]

(여기서,

임),

(here,

being),

(ii) forming a transition metal compound comprising an unsaturated double bond;

(iii) 1 to 30% by weight of the transition metal compound containing the unsaturated double bond, 15 to 35% by weight of the radical polymerizable unsaturated monomer, 5 to 20% by weight of the aromatic hydrocarbon solvent, 1 to 10% by weight of the chain transfer agent, initiator 1 Mixing 10 wt% to 10 wt% to form an intermediate; And

(iv) 5 to 25% by weight of the carboxylic acid-containing ester compound represented by Formula 1 in the intermediate, 8 to 20% by weight of monobasic organic acid, 1 to 20% by weight of metal oxide, 1 to 10% by weight of alcohol, 0.5 distilled water It provides a method for producing an antifouling paint composition comprising;

When the binder using the ester compound according to the present invention is used, the following effects can be obtained.

First, it is possible to obtain the effect of improving the flexibility and material adhesion of the coating film by controlling the molecular weight of the ester compound, thereby preventing the coating film from breaking and peeling.

Second, by controlling the molecular weight of the ester compound can improve the hardness of the coating film and increase the antifouling performance by increasing the hydrolysis rate.

Third, more various antifouling paints can be designed by introducing a synthetic technique capable of appropriately controlling the amount and type of molecular weight and polar groups. In general, the introduction of a limited structure and molecular weight can not guarantee a long-term stable antifouling performance due to non-uniform wear, in the present invention, it is possible to introduce ester compounds of various molecular weight in the introduction of ester compounds, hydrophilic ester compounds -By adjusting HLB (Hydrophilic-Lipophilic Balance), it is possible to secure a uniform wear rate in the long term, and thus obtain excellent long-term antifouling performance.

Fourth, by using an ester compound containing at least two or more ethers and ester groups through a two-step reaction of the ester compound, non-paired electron pairs of ether and ester groups become complexes to the metal, thereby improving stabilization of the metal, and consequently, storage stability The effect can be improved.

Fifth, since the metal complex compound formed in the present invention is present in the form of being bonded to the polymer chain, it prevents non-uniform and partial gelation and uniform distribution of the metal complex compound. And flaking phenomenon can be prevented.

Hereinafter, the present invention will be described in more detail.

The present invention provides an antifouling coating composition comprising a binder resin, a metal oxide, and an organic antifouling agent, wherein the binder resin (A) has a branched structure in which a hydroxyl group of a polyhydric alcohol terminal is combined with at least one selected from fatty acids and acid anhydrides. Ester compound containing the carboxyl group represented by General formula (1) which has;

[Formula 1]

(여기서,

임),

(here,

being),

(B) a transition metal-containing ester compound represented by the following formula (2);

[Formula 2]

(C) a transition metal compound containing an unsaturated double bond; And (D) an antifouling coating composition obtained by copolymerizing a radically polymerized monomer containing an unsaturated double bond,

X is an alkyl group or cycloalkyl group having 2 to 15 carbon atoms, Y is an alkylene or polyalkyl ether group having 2 to 8 carbon atoms, Z is an alkyl group having 2 to 12 carbon atoms, m, n is an integer of 1 to 8 , Wherein M is a metal element and R ₄ is a monobasic organic acid provides an antifouling coating composition.

The ester compound (A) containing a carboxyl group represented by the formula (1) is preferably an acid anhydride or an acid acid, 40 to 52% by weight, after mixing 18 to 30% by weight of a polyhydric alcohol having 2 to 10 carbon atoms, further acid anhydride It is a compound obtained by reacting 18-30 weight%.

The ester compound containing a carboxyl group represented by the formula (1) uses an ester compound containing at least two ethers and ester groups, so that the non-covalent electron pairs of ether and ester groups become complexes to the metal, thereby improving stabilization of the metal, and consequently storing The effect of improving stability can be obtained.

If the weight average molecular weight of the ester compound (A) containing a carboxyl group represented by the formula (1) is increased, the flexibility and material adhesion of the coating film can be improved, while the hydrolysis rate is reduced due to the increase in hydrophobicity. It can cause performance degradation. In addition, when the weight average molecular weight is reduced, the hardness of the coating film may be improved, and the antifouling performance may be induced by increasing the hydrolysis rate, but crack resistance may be deteriorated. The present invention can introduce a two-step reaction that can overcome the disadvantages of the prior art by introducing a synthetic technology that can appropriately control the amount and type of molecular weight, polar groups can be designed more various antifouling paints.

The ester compound (A) containing a carboxyl group represented by the formula (1) having a branched structure in which a hydroxyl group of a polyhydric alcohol terminal is bonded to at least one selected from fatty acids and acid anhydrides, preferably has a weight average molecular weight of 550 to 1300, More preferably, it is 550-1000, Most preferably, it is 550-850. If the weight average molecular weight is less than 550, it is not preferable because the wear rate is too fast and cracks may occur. If the weight average molecular weight exceeds 1300, the wear rate is too slow and the tacky phenomenon of the dryness of the coating film is undesirable.

The ester compound (A) having a branched structure in which a hydroxy group at the polyhydric alcohol terminal is bonded to at least one selected from fatty acids and acid anhydrides, wherein the hydroxy group at the polyhydric alcohol terminal is combined with a fatty acid and / or an acid anhydride, specifically, a hydroxy group The branched structure in which the fatty acid / acid anhydride is couple | bonded at one or both ends is shown. Fatty acids / acid anhydrides which are bound to the hydroxy of polyhydric alcohols can be bound in various forms, the structures of which are not linear but in the form of chains or reticulated forms.

According to the present invention, the ester compound represented by the formula (A) is a condensation reaction of a saturated acid and alcohol containing a carboxyl group, a condensation reaction of an acid anhydride and an alcohol, or a condensation reaction of a saturated acid and an acid anhydride containing an carboxyl group and an alcohol. The reaction molar ratio of the acid (saturated acid, acid anhydride) and the alcohol as the carboxylic acid-containing ester compound obtained through is preferably 1: 1 to 1: 3, more preferably 1: 1 to 1: 2. That is, the saturated acid and the acid anhydride are reacted with the number of moles corresponding to the number of hydroxyl groups of the polyhydric alcohol.

Acid anhydrides include adipic acid, terephthalic acid, succinic anhydride, maleic anhydride, phthalic anhydride, tetraphthalic anhydride, citraconic anhydride, itaconic anhydride, hexahydrophthalic anhydride, 4-methyltetraphthalic anhydride, 4-methylhexahydrophthalic anhydride And at least one selected from the group consisting of 3-methyltetrahydrophthalic anhydride.

The polyhydric alcohol is preferably at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol, glycerin, trimethylolpropane, and pentaerythritol. .

The monobasic organic acid is preferably at least one selected from the group consisting of acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, linoleic acid, naphthenic acid, octanoic acid, oleic acid, chloroacetic acid, fluoroacetic acid and valeric acid having 1 to 20 carbon atoms. Do.

In the present invention, since the reaction rate varies depending on the type and molar ratio of the saturated acid, acid anhydride and the organic compound having an ether group to be reacted, it is necessary to appropriately control the reaction temperature according to the reactant and the molar ratio.

By using a variety of antifouling paints using the magnetic wear binder according to the present invention, it is possible to obtain the effect of improving the flexibility and material adhesion of the coating film by controlling the molecular weight of the ester compound, thereby preventing the coating film from breaking and peeling. Can be. In addition, by controlling the molecular weight, it is possible to improve the hardness of the coating film and increase the antifouling performance by increasing the hydrolysis rate, and uniform wear rate due to the hydrophilic-lipophilic balance (HLB) control of various ester compounds. By ensuring the long-term antifouling performance can be guaranteed.

The transition metal-containing ester compound (B) represented by Formula 2 may be formed by combining a transition metal with a monobasic organic acid. In the binder according to the present invention, the monobasic organic acid may be present in the form of Chemical Formula 2, or may be present as a monobasic organic acid alone.

[Formula 2]

M is a metal element and R ₄ is a monobasic organic acid.

The metal element is preferably selected from the group consisting of iron, nickel, platinum, copper, zinc, mercury, aluminum, silicon and tellurium. The monobasic organic acid may be acetic acid having 1 to 20 carbon atoms, propionic acid, butyric acid, lauric acid, stearic acid, linoleic acid, naphthenic acid, octanoic acid, oleic acid, chloroacetic acid, fluoroacetic acid, valeric acid and the like.

The transition metal compound (C) containing an unsaturated double bond may be represented by the following Chemical Formula 3 or 4:

Wherein M is a metal element and R ₂ is H, a methyl group.

In addition, (D) the radically polymerized monomer containing an unsaturated double bond may be represented by the following formula (5):

In the above formula, R ₂ is H, a methyl group, and R ₃ is an alkyl group having 1 to 8 carbon atoms.

The transition metal compound (C) including an unsaturated double bond and the radical polymerized monomer (D) including an unsaturated double bond may include an ester compound (A) or a monobasic organic acid including a carboxyl group in the copolymerization process. For example, it may be represented by the formula (6) or (7).

Wherein M is a metal element, R ₂ is H, a methyl group, R ₄ is an organic acid, and R ₅ is an ester compound (A) containing a carboxyl group represented by formula (1).

Since the metal complex formed in the present invention is present in the form of being bonded to the polymer chain, it prevents non-uniform and partial gelation and uniform distribution of the metal complex, so that cracks, peels, and plays during long exposures FLAKING can be prevented.

According to another aspect of the present invention, in the method for producing an antifouling paint composition containing a binder resin, a metal oxide, and an organic antifouling agent, the binder resin includes (i) a saturated acid containing a carboxyl group and a polyhydric acid having 2 to 10 carbon atoms. Synthesizing a carboxylic acid-containing ester compound represented by Formula 1 obtained through condensation of alcohol or condensation of an acid anhydride with the polyhydric alcohol;

[Formula 1]

(여기서,

이고, 상기 X는 탄소수 2 ~ 15의 알킬기 또는 시클로알킬기이고, Y는 탄소수 2 ~ 8의 알킬렌 또는 폴리알킬에테르기이고, Z는 탄소수 2 ~ 12의 알킬기이고, m, n은 1 ~ 8의 정수임),

(here,

X is an alkyl group or cycloalkyl group having 2 to 15 carbon atoms, Y is an alkylene or polyalkyl ether group having 2 to 8 carbon atoms, Z is an alkyl group having 2 to 12 carbon atoms, and m and n are 1 to 8 carbon atoms. Integer),

(ii) forming a transition metal compound comprising an unsaturated double bond; (iii) 1 to 30% by weight of the transition metal compound containing the unsaturated double bond, 15 to 35% by weight of the radical polymerizable unsaturated monomer, 5 to 20% by weight of the aromatic hydrocarbon solvent, 1 to 10% by weight of the chain transfer agent, initiator 1 Mixing 10 wt% to 10 wt% to form an intermediate; And (iv) 5 to 25% by weight of the carboxylic acid-containing ester compound represented by Formula 1 in the intermediate, 8 to 20% by weight of monobasic organic acid, 1 to 20% by weight of metal oxide, 1 to 10% by weight of alcohol, distilled water It provides a method for producing an antifouling paint composition comprising; mixing 0.5 to 5.0% by weight.

First, the step (i) of synthesizing the carboxylic acid-containing ester compound (A) represented by Formula 1 is as follows.

The monobasic organic acid and polyhydric alcohol are mixed and the reaction temperature is maintained at 100 to 250 ° C in the absence of a solvent. The end point of the reaction is determined by measuring the acid value (solid dispersion value = 15 mg KOH / g or less), and reacted for several hours to synthesize a primary product.

The monobasic organic acid is preferably acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, linoleic acid, naphthenic acid, octanoic acid, oleic acid, chloroacetic acid, fluoroacetic acid, valeric acid and the like.

The content of monobasic organic acid is preferably 40 to 52% by weight. When the monobasic organic acid content is less than 40% by weight, the wear rate of the resin is slowed down, and when it exceeds 52% by weight, the wear rate of the resin is increased, but the coating film is brittle, and thus the crack resistance tends to be poor. Not desirable

The polyhydric alcohol is preferably at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol, glycerin, trimethylolpropane, and pentaerythritol. .

In addition, the content of the polyhydric alcohol is preferably 18 to 30% by weight. If the polyhydric alcohol content is less than 18% by weight, the molecular weight of the resin is lowered to brittle the coating film. If the polyhydric alcohol content is higher than 30% by weight, the molecular weight of the resin is increased to soften the coating film. Because it is not desirable.

Subsequently, the acid anhydride was mixed with the first obtained product and reacted for several hours to obtain a compound represented by Chemical Formula 1 having an acid value of 100 to 150 mg KOH / g and a solid content of 93% by weight or more. Acid anhydrides include adipic acid, terephthalic acid, succinic anhydride, maleic anhydride, phthalic anhydride, tetraphthalic anhydride, citraconic anhydride, itaconic anhydride, hexahydrophthalic anhydride, 4-methyltetraphthalic anhydride, 4-methylhexahydrophthalic anhydride , 3-methyltetrahydrophthalic anhydride and the like are preferable.

And, the content of the acid anhydride is preferably 18 to 30% by weight. If the acid anhydride content is less than 18% by weight, the wear rate of the resin is lowered, and if it exceeds 30% by weight, it is not preferable because the wear rate of the resin is too high to cause flakes of the antifouling coating film.

Step (ii) to prepare a transition metal compound containing an unsaturated double bond is as follows. A mixture of a compound having a carboxyl group, such as a monobasic organic acid, and water was added to the mixture of an organic solvent and a metal oxide at constant speed. After further stirring, an organic solvent is added to obtain a clear mixture solution containing a transition metal compound containing an unsaturated double bond. The transition metal compound containing an unsaturated double bond may be represented by Formula 3 or Formula 4:

(3)

,

,

[Formula 4]

Wherein M is a metal element and R ₂ is H, a methyl group.

In addition, the radical polymerizable unsaturated monomer may be represented by the following Chemical Formula 5:

[Chemical Formula 5]

In the above formula, R ₂ is H, a methyl group, and R ₃ is an alkyl group having 1 to 8 carbon atoms.

The transition metal compound including an unsaturated double bond and the radical polymerized monomer including an unsaturated double bond may include an ester compound (A) and / or a monobasic organic acid including a carboxyl group in the copolymerization process, for example. It may be represented by the formula (6) or formula (7).

[Formula 6]

,

,

[Formula 7]

Wherein M is a metal element, R ₂ is H, a methyl group, R ₄ is an organic acid, and R ₅ is an ester compound (A) containing a carboxyl group represented by formula (1).

And (iii) to prepare an intermediate by copolymerizing the already obtained transition metal compound containing an unsaturated double bond and a radical polymerized monomer containing an unsaturated double bond. Specifically, the temperature is increased while stirring by adding an organic solvent and an aromatic hydrocarbon solvent.

The content of the transition metal compound containing an unsaturated double bond is preferably 1 to 30% by weight. When the content of the transition metal compound containing an unsaturated double bond is less than 1% by weight, the wear rate decreases, and the antifouling performance of the paint decreases. When the content of the transition metal compound exceeds 30% by weight, the wear rate increases, but the coating film is increased due to the increased crosslinking between the metal oxides. The crack resistance of the resin becomes poor and the reaction viscosity becomes difficult due to the increase of the reaction viscosity of the resin.

And the content of the radically polymerizable unsaturated monomer compound is preferably 15 to 35% by weight. If the content of the radically polymerizable unsaturated monomer compound is less than 15% by weight, the adhesion of the antifouling paint is inferior, and if it exceeds 35% by weight, it is not preferable because the uniform antifouling property of the antifouling paint is difficult to exhibit.

Subsequently, a mixture of a transition metal compound, an aromatic hydrocarbon solvent, a chain transfer agent, and an initiator containing an unsaturated double bond prepared by mixing a radically polymerizable unsaturated monomer was reacted. t-butylperoxy acetate and the aromatic hydrocarbon solvent were added dropwise, and the mixture solution obtained after stirring at the same temperature was further identified as an intermediate resin composition. Preferably Gardner viscosity (Gardner viscosity) Z3 ~ Z5, solid content 43.5 ± 1.0% by weight and is colorless and transparent.

In this copolymerization reaction, it is also preferable to use a chain transfer agent. This is to improve the uniform wear performance of the antifouling coating film and to maintain the antifouling performance for a long time. It is preferable to use a chain transfer agent other than mercaptan as the chain transfer agent from the viewpoint of compatibility with the polymerizable unsaturated monomer containing a metal. For example, styrene dimer or the like can be used.

In the present invention, in order to improve uniform wear and long-term antifouling performance of the coating film, preferably, 1 to 10% by weight of a chain transfer agent and 1 to 5% by weight of a polymerization initiator may be used.

Finally, the ester compound (A) containing carboxylic acid, monobasic organic acid, metal oxide, polyhydric alcohol, and distilled water were added to the intermediate resin composition, and the temperature was raised to 90 ° C. and maintained at the same temperature for several hours. The step (iv) is carried out to obtain a resin composition containing the copolymer. The reaction is 5 to 25% by weight of the carboxylic acid-containing ester compound represented by Formula 1, 8 to 20% by weight of monobasic organic acid, 1 to 20% by weight of metal oxide, 1 to 10% by weight of alcohol, 0.5 to 5.0% by weight of distilled water It is preferable to include.

The content of monobasic organic acid is preferably 8 to 20% by weight, more preferably 8 to 17% by weight. If the monobasic organic acid content is less than 8% by weight, the wear performance is lowered, which is not preferable. If the content of the monobasic organic acid is more than 20% by weight, the uniform wear performance of the resin is lowered, and in severe cases, flakes of the antifouling coating film are generated. It is not preferable because it is.

Example

Preparation of ester compound (A) represented by formula (1)

In a four-necked round flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, 315 g of naphthenic acid and octanoic acid and 160 g of a polyhydric alcohol as described in Table 1 were mixed, and then heated to 210-230 ° C. to maintain the reaction. The end point of the reaction was determined by measuring the acid value (solid dispersion value = 15 mg KOH / g or less), and reacted for 5 hours to synthesize a primary obtained. After the first reaction, 135 g of adipic acid, phthalic anhydride, and 3-methyltetrahydrophthalic anhydride were mixed in a flask cooled to 150 ° C., and reacted at 130 ° C. for 3 hours to give an acid value of 100 to 150 mg KOH / g, The ester compound (A) represented by General formula (1) whose solid content is 93 weight% or more was obtained.

The compound of formula (1)  Molecular Weight Polyhydric alcohol A-1 250-500 Diethylene glycol A-2 550-850 Diethylene glycol, glycerin A-3 1000-1300 Glycerin, Pentaerythritol

Preparation of Transition Metal Compounds Containing Unsaturated Double Bonds

A four-necked round flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube was filled with 55 parts of propylene glycol monobutyl ether and 70 parts of zinc oxide, and heated to 85 ° C while stirring. Subsequently, the mixture which consists of 80 parts of acrylic acid and methacrylic acid and 10 parts of water was dripped at constant speed from the dripping funnel for 3 hours. After completion of the dropwise addition, the reaction solution became clear from the milky white state. After stirring for further 2 hours, 95 parts of propylene glycol monobutyl ether was added to obtain a transparent mixture solution containing a zinc compound containing an unsaturated double bond. Solid content (zinc-containing monomer) in the obtained mixture solution was 50.0 weight%.

Preparation of Copolymer Binder

A four-necked round flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube was charged with 135.24 parts of propylene glycol monobutyl ether and 840 parts of xylene and heated to 107 ° C while stirring. Subsequently, 250 parts of methyl methacrylate, 120 parts of butyl acrylate, 185 parts of ethyl acrylate, 100 parts of 2-ethylhexyl acrylate, and 215 parts of methacrylic acid were mixed to form 880 parts from the dropping funnel, and the prepared unsaturated double bond was prepared. A transparent mixture consisting of 953.4 parts of a zinc compound solution to be contained, 347.13 parts of xylene, 132.3 parts of altamethylstyrene dimer, and 144.9 parts of BPO (benzoyl peroxide) was added dropwise at 5 hours. After completion of the dropwise addition, a holding reaction was carried out for 1 hour, 5.33 parts of t-butylperoxy acetate and 63 parts of aromatic hydrocarbon-based solvent were added dropwise for 30 minutes, and further stirred for 1 hour and 30 minutes at the same temperature. A colorless and transparent resin composition having a Gardner viscosity of Z3 to Z5 and a solid content of 43.5 ± 1.0 wt% was identified and cooled to 80 ° C.

350 parts of the ester compounds shown in Table 1, 370 parts (8% by weight) of naphthenic acid and octanoic acid, 550 parts (12% by weight), 800 parts (17% by weight) of zinc oxide 168 parts, butanol 210.84 parts, distilled water 37.13 After adding the parts, the mixture was heated to 90 ° C. and maintained at the same temperature for 4 hours, thereby obtaining a yellowish-transparent zinc-containing copolymer resin composition in which the resin composition had a Gardner viscosity of H to N and a solid content of 51 ± 2.0 wt%.

bookbinder
compound Reactant Ester compound
(A) Monobasic Organic Acid Content
(weight%) Component E-1 Component A-1 8 Component E-2 Component A-1 12 Component E-3 Component A-1 17 Component E-4 Component A-2 8 Component E-5 Component A-2 12 Component E-6 Component A-2 17 Component E-7 Component A-3 8 Component E-8 Component A-3 12 Component E-9 Component A-3 17 Comparative E-10 Component A-2 0 Comparison E-11 none 12

Antifouling paint  Preparation of the composition

Preparation of the antifouling coating composition comprises 35 parts by weight of zinc-containing copolymer (E) and 40 parts by weight of iron oxide, zinc oxide, talc, organic antifouling agent, thixotropic agent, additives, and zylene as shown in Table 3, respectively. After mixing and dispersing by stirring at a rotation speed of 2,500 rpm using a disperser, it was prepared by filtration using a 100 mesh filter.

Antifouling paint  Performance Evaluation of Composition

The antifouling paints were prepared by the formulation of Table 3 using the binders of the preparation examples of Table 2, and the antifouling performance and the wear performance of each paint were evaluated.

Antifouling performance  Evaluation and Results

After painting the antifouling paint composition on the horizontal x vertical x thickness 100mm x 300mm x 2mm PVC board, respectively, front and back on both sides, and drying them for a week, they were deposited at 1.5m below the sea surface of Suyeong Bay, Dadaepo, and Malaysian sea. Antifouling performance was confirmed.

A: No attachment of animals and plants

B: Thin slime layer observed on the surface of coating, no adhesion of animals and plants

C: Observation of thick slime layer on the surface of coating film or occurrence of plant adhesion of less than 20% of the effective area of specimen, no adhesion of animals

D: Occurrence of plant adhesion less than 50% of specimen effective area, no animal adhesion

E: Occurrence of plant attachment or animal attachment to the entire specimen effective area

Table 4 shows the evaluation results of the antifouling performance.

As shown in Table 4 above, the antifouling paint of the present invention prepared by containing the component A-2 in the compound of Formula 1 may provide excellent antifouling performance over a long period of time, and the components A-1 and A-3. Antifouling paints, including that can be seen that the relatively poor antifouling performance. In addition, it can be seen that the paint that does not contain any one of the ester compound (A) and monobasic organic acid is significantly reduced antifouling performance.

Wear Performance Evaluation and Results

Abrasion performance is applied to the anti-fouling paint composition on a PVC disc with a circumference of 200 mm and rotated at a speed of 15 knots to measure the abrasion thickness of the coating film for 6 months at intervals of one month. It measured and compared and confirmed. Table 5 shows the evaluation results of the wear performance.

1 month 2 months 3 months 4 months 5 months 6 months Average room Example One 13.9 10.2 11.1 10.3 10.0 Crack 2 14.2 11.8 11.9 12.1 11.8 Crack 3 14.3 14.1 13.2 Crack 4 15.2 14.5 14.3 Crack 5 15.8 14.8 Crack 6 16.2 15.1 Crack 7 9.8 8.5 8.5 8.1 8.7 7.9 8.59 8 10.6 9.1 9.2 9.0 8.8 8.7 9.23 9 10.5 10.9 10.1 9.5 9.4 10.1 10.09 10 11.3 12.0 11.5 11.6 11.3 10.2 11.32 11 12.8 10.8 11.5 10.9 12.0 11.9 11.65 12 13.5 13.8 12.9 13.2 13.0 13.5 13.32 13 8.1 5.2 5.6 5.4 6.0 5.0 5.88 14 9.6 6.6 6.9 7.1 6.1 6.0 7.05 15 9.5 6.1 7.2 7.6 7.7 7.0 7.52 16 11.3 7.2 7.8 6.0 7.2 7.6 7.85 17 10.5 7.5 7.4 8.0 7.1 7.3 7.97 18 11.8 8.8 8.4 8.3 7.7 7.5 8.75 Comparative example 19 5.2 4.5 4.8 4.9 5.1 4.6 4.85 20 6.6 6.1 7.0 6.3 5.2 5.8 6.17 21 18.1 Crack - - - - 22 20.2 Crack - - - -

Referring to Table 5, it can be seen that a constant wear rate can be maintained in paints containing component A-2 in the compound of Formula 1 and containing an appropriate monobasic organic acid. You can see the import.

In the compound of Formula 1, component A-1 exhibited a high wear rate and cracks in the coating after a long time. In the comparative example, the coating material containing no monobasic organic acid was found to have a low wear rate, and the coating material containing no ester compound (A) was found to have a high wear rate and cracking of the coating film.

The antifouling paint of the present invention contains component A-2 in the compound represented by Formula 1 to prevent cracking of the coating film, and to provide uniform wear performance and excellent performance. By developing an antifouling coating composition having antifouling performance, it can be seen that it is suitable as a substitute for the conventional antifouling coating composition.

Claims (13)

In the antifouling coating composition comprising a binder resin, a metal oxide, and an organic antifouling agent, the binder resin is
(A) an ester compound containing a carboxyl group represented by the formula (1) having a branched structure in which a hydroxyl group of a polyhydric alcohol terminal is bonded with at least one selected from fatty acids and acid anhydrides;
[Formula 1]

(here,

being),
(B) a transition metal-containing ester compound represented by the following formula (2);
(2)

(C) a transition metal compound containing an unsaturated double bond; And
(D) An antifouling coating composition characterized by being obtained by copolymerizing a radically polymerized monomer containing an unsaturated double bond,
X is an alkyl group or cycloalkyl group having 2 to 15 carbon atoms, Y is an alkylene or polyalkyl ether group having 2 to 8 carbon atoms, Z is an alkyl group having 2 to 12 carbon atoms, m, n is an integer of 1 to 8 ,
M is a metal element, R ₄ is a monobasic organic acid antifouling paint composition.
The method of claim 1,
(A) the ester compound represented by Formula 1 is 40 to 52% by weight of an acid anhydride or an organic acid,
It is a compound obtained by mixing 18-30 weight% of C2-C10 polyhydric alcohols, and then reacting 18-30 weight% of acid anhydrides.
The method of claim 1,
(A) The antifouling coating composition characterized in that the ester compound represented by the formula (1) has a weight average molecular weight of 550 to 1000.
The method of claim 2,
The acid anhydride is adipic acid, terephthalic acid, succinic anhydride, maleic anhydride, phthalic anhydride, tetraphthalic anhydride, citraconic anhydride, itaconic anhydride, hexahydrophthalic anhydride, 4-methyl tetraphthalic anhydride, 4-methylhexahydrophthalic anhydride An antifouling coating composition, characterized in that at least one selected from the group consisting of anhydride, and 3-methyltetrahydrophthalic anhydride.
The method of claim 2,
The polyhydric alcohol is at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol, glycerin, trimethylolpropane, and pentaerythritol Antifouling coating composition.
The method of claim 1,
The monobasic organic acid is one or more selected from the group consisting of acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, linoleic acid, naphthenic acid, octanoic acid, oleic acid, chloroacetic acid, fluoroacetic acid, valeric acid having 1 to 20 carbon atoms Antifouling coating composition characterized in that.
The method of claim 1,
The transition metal compound containing the (C) unsaturated double bond is an antifouling coating composition characterized in that represented by the following formula (3) or (4):
(3)

,
[Chemical Formula 4]

In the above formula, R ₂ is H, a methyl group.
The method of claim 1,
The radically polymerized monomer containing the (D) unsaturated double bond is an antifouling coating composition, characterized in that represented by the following formula (5):
[Chemical Formula 5]

In the above formula, R ₂ is H, a methyl group, and R ₃ is an alkyl group having 1 to 8 carbon atoms.
In the method for producing an antifouling coating composition comprising a binder resin, a metal oxide, and an organic antifouling agent, the binder resin is
(i) a condensation reaction of a saturated acid containing a carboxyl group with a polyhydric alcohol or acid anhydride having 2 to 10 carbon atoms and the polyhydric alcohol is combined with one or more selected from fatty acids and acid anhydrides to form a branched structure. Synthesizing a carboxylic acid-containing ester compound represented by Formula 1;
[Formula 1]

(here,

X is an alkyl group or cycloalkyl group having 2 to 15 carbon atoms, Y is an alkylene or polyalkyl ether group having 2 to 8 carbon atoms, Z is an alkyl group having 2 to 12 carbon atoms, and m and n are 1 to 8 carbon atoms. Is an integer.)
(ii) forming a transition metal compound comprising an unsaturated double bond;
(iii) 1 to 30% by weight of the transition metal compound containing the unsaturated double bond, 15 to 35% by weight of the radical polymerizable unsaturated monomer, 5 to 20% by weight of the aromatic hydrocarbon solvent, 1 to 10% by weight of the chain transfer agent, initiator 1 Mixing 10 wt% to 10 wt% to form an intermediate; And
(iv) 5 to 25% by weight of the carboxylic acid-containing ester compound represented by Formula 1 in the intermediate, 8 to 20% by weight of monobasic organic acid, 1 to 20% by weight of metal oxide, 1 to 10% by weight of alcohol, 0.5 distilled water Method for producing an antifouling paint composition comprising;
10. The method of claim 9,
The ester compound containing a carboxyl group represented by Formula 1 is 40 to 50% by weight of an acid anhydride or an organic acid,
18 to 30% by weight of a polyhydric alcohol having 2 to 10 carbon atoms, and then a compound obtained by reacting 18 to 30% by weight of an acid anhydride.
10. The method of claim 9,
Ester compound containing a carboxyl group represented by the formula (1) is a method for producing an antifouling paint composition, characterized in that the weight average molecular weight of 550 to 1300.
10. The method of claim 9,
Method for producing an antifouling coating composition characterized in that the transition metal compound containing the unsaturated double bond is represented by the following formula (3) or (4):
(3)

,
[Chemical Formula 4]

Wherein M is a metal element and R ₂ is H, a methyl group.
10. The method of claim 9,
The radically polymerizable unsaturated monomer is a method for producing an antifouling paint composition, characterized in that represented by the following formula (5):
[Chemical Formula 5]

In the above formula, R ₂ is H, a methyl group, and R ₃ is an alkyl group having 1 to 8 carbon atoms.