KR20120111064A - Binder for anti-fouling paint, method for preparing the same, and anti-fouling paint composition comprising the same - Google Patents

Abstract

PURPOSE: A manufacturing method of anti-fouling binder fouling paint is provided to reduce production time of an anti-fouling binder, and to provide an anti-fouling binder capable of providing high solid concentration to anti-fouling paint and obtaining workability and physical properties same with existing one. CONSTITUTION: A manufacturing method of anti-fouling binder fouling paint comprises: a step of preparing a medium represented by chemical formula 1-3 by reacting a monomer containing a double bond and carboxy group and/or low molecular weight organic acid with divalent metal; and a step of copolymerizing the medium and a radically polymerizable monomer. In chemical formulas, R^1, R^3 and R^4 is respectively and independently H or CH3, R^2, R^5 and R^6 is respectively and independently an organic group. M is the divalent group.

Description

Binder for antifouling paints, preparation method thereof, and antifouling paint composition comprising same {BINDER FOR ANTI-FOULING PAINT, METHOD FOR PREPARING THE SAME, AND ANTI-FOULING PAINT COMPOSITION COMPRISING THE SAME}

The present invention relates to a binder for an antifouling paint, a method of manufacturing the same, and an antifouling paint composition comprising the same, and more particularly, to prepare the overall intermediate by preferentially preparing an intermediate having a specific structure when preparing a binder used in a hydrolytic antifouling paint. A binder for antifouling paints, a method for manufacturing the same, and an antifouling paint composition including the same, which can shorten time and impart high solids content to the antifouling paint including the binder thus prepared, while ensuring the same workability and physical properties as before. will be.

The coating composition to which the antifouling resin is applied is a top coat of a coating film coated on a ship's hull outside and an underwater structure to prevent the adhesion and growth of marine organisms that cause surface contamination of the seawater deposition coating, The control is for that purpose. When various marine organisms are attached to the surface of the coating, the frictional force between the surface of the coating and the seawater may increase during the operation of the ship, thereby greatly increasing the fuel cost, which accounts for a large portion of the operating expenses. Antifouling paint is a paint to remove these attachments and to reduce the coefficient of friction between water and ship during operation.

There are two types of antifouling paints: an insoluble type using an insoluble binder and a water-soluble type using a water-soluble binder. The insoluble type was applied to antifouling paints of the old generation. It is an antifouling paint in which a large amount of antifouling agent such as copper oxide is added to vinyl and rubber chloride resin which are not soluble in water. Antifouling agents, such as copper nitrous oxide, are gradually diffused into the seawater to exhibit antifouling performance. The water-soluble type is a paint mixed with an insoluble resin and a water-soluble resin (eg, rosin) and used with an antifouling agent. As the resin is dissolved in water, the antifouling agent present in the coating film comes out of the seawater and exhibits antifouling performance. The water-soluble type has a longer antifouling performance than the insoluble type, but the coating film does not melt uniformly, and the antifouling performance is exhibited for a maximum of 3 years.

The self-wear antifouling paint widely used at present is a method in which an insoluble resin encounters seawater, hydrolysis occurs, and gradually changes to water solubility to release antifouling agents such as copper nitrous oxide to exhibit antifouling performance. Compared with the existing water-soluble type, the melting rate in sea water is controlled uniformly, so it can exhibit long-term antifouling performance.

Self-wear antifouling paints can be divided into tin-based and non-tin based on the presence or absence of tin-based materials, and non-tin-based can be further divided into metal and silyl types. The tin type is a structure in which tributyl tin oxide is chemically bonded to an acrylic main chain, and is hydrolyzed in an alkali of pH 8 or higher to be a copolymer of acrylic acid, and gradually dissolved in weak alkali seawater. In particular, hydrolyzed tributyl tin has a combination of self-wear resistance and antifouling properties. However, due to tributyl tin poisoning, negative factors such as malformation of fish and maleization of females were highlighted, and regulations were introduced in 2003, and their use was banned from January 2008.

The metal type of the non-tin type has a structure similar to that of the tin type. Zn, Cu, etc. are bonded to acrylic acid or acid compound, and are dissolved in seawater due to hydrolysis. Since the non-tin metal type does not have antifouling property of its own, it is merely responsible for controlling abrasion through hydrolysis and imparts antifouling property by adding a separate organic and inorganic antifouling agent.

Among the non-tin-based silyl types, the chemical stability is high, so that various antifouling agents can be used, and the wear rate is more stable than the non-tin metal type. However, since the silyl type acrylic monomer is expensive, the overall raw material cost is high, and the wear rate at the time of anchoring is low, so that the antifouling property is not sufficient.

U.S. Patent 5,199,977 describes a technique for introducing compounds such as non-volatile amines, alcohols, ureas and phenols as ligands for stabilization and low viscosity of metals in metal ester containing binder structures. However, these amines have too low solubility in water as compared to the binder, resulting in a rapid decrease in the wear rate of the binder over time. In addition, cracks may occur at seawater lines when exposed for long periods of time. Ligands such as phenols, ureas and alcohols described together are relatively poor in water resistance and may cause swelling, flaking and discoloration of the coating film.

The present invention has been made to solve the problems of the prior art as described above, while reducing the manufacturing time, it is possible to ensure the same workability and physical properties as the conventional and the antifouling paint binder that can impart a high solids content to the antifouling paint And it is a technical subject to provide the manufacturing method.

In order to achieve the above technical problem, the present invention (a) a monomer containing a double bond and a carboxyl group, or a low molecular weight organic acid or both and reacted with a divalent metal to an intermediate represented by any one of the following formula (1) Manufacturing; And (b) copolymerizing the intermediate with the radical polymerizable monomer.

[Formula 1]

[Formula 2]

(3)

(Wherein R ¹ , R ³ and R ⁴ each independently represent H or CH ₃ ; R ² , R ⁵ and R ⁶ each independently represent an organic group; M represents a divalent metal.)

In addition, another aspect of the present invention provides a binder prepared according to the above method and an antifouling coating composition comprising the same.

Using the production method of the present invention can significantly shorten the manufacturing time of the antifouling paint compared to the prior art, while maintaining the high solid content, the workability, It is possible to provide an antifouling paint having excellent antifouling properties, wear rate, and crack resistance.

Hereinafter, the present invention will be described in detail.

[ Antifouling paint  Preparation of Binder]

(a) intermediate manufacturing step

In the production method of the antifouling paint binder, a hydrolyzable compound represented by any one of the following Chemical Formulas 1 to 3 is made by reacting a monomer containing a double bond and a carboxyl group, a low molecular weight organic acid, or both and a divalent metal. After preparing the intermediate first, it is characterized in that it is used in the secondary reaction. By first preparing the intermediate of the specific structure as described above, the overall binder manufacturing time can be greatly shortened.

[Formula 1]

[Formula 2]

(3)

Wherein R ¹ , R ³ and R ⁴ each independently represent H or CH ₃ , and R ² , R ⁵ and R ⁶ each independently represent an organic group (eg, an aliphatic, alicyclic and aromatic hydrocarbon group). . Preferred organic groups are C ₁ Saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbons of ~ C _{24 And} the like, but is not necessarily limited thereto. On the other hand, M represents a divalent metal (eg, zinc, copper, iron, titanium, calcium, and the like).

The intermediate of Formula 1 may be prepared by reacting a double bond, a monomer containing a carboxyl group, a divalent metal, and a low molecular weight organic acid under an appropriate temperature. In this case, intermediates of Chemical Formulas 2 and 3 may be prepared in addition to Chemical Formula 1 according to the molar ratio of the double bond and the carboxyl group-containing monomer, the divalent metal, and the low molecular weight organic acid. Specifically, when the (mole) equivalent ratio of the monomer: divalent metal: low molecular weight organic acid containing a double bond and a carboxyl group is 1: 1, an intermediate of the structure shown in Chemical Formula 1 is prepared, and contains a double bond and a carboxyl group. The larger the proportion of the monomer is prepared an intermediate of the structure as shown in Formula 2, the higher the proportion of the low molecular weight organic acid is prepared an intermediate of the structure as shown in Formula 3.

The stoichiometric amounts of the intermediates represented by Formulas 1, 2, and 3 follow Formulas 1, 2, and 3, and examples thereof are shown in Table 1 below.

[Formula 1]

A = Y-(| X-Z | / 2)

[Formula 2]

B = (X-(Y-| X-Z | / 2)) / 2

[Equation 3]

C = (Z-(Y-| X-Z | / 2)) / 2

Wherein A, B, C, X, Y and Z each represent:

A: stoichiometric ratio (mol) in which the intermediate of Formula 1 is produced

B: stoichiometric ratio (molar) from which the intermediate of Formula 2 is produced

C: stoichiometric ratio (mol) in which the intermediate of Formula 3 is produced.

X: amount of monomer containing a double bond and a carboxyl group (mol)

Y: amount of divalent metal (mol)

Z: Amount (mol) of low molecular weight organic acid

Table 1 Intermediate Preparation Type According to Monomer Equivalence Ratio

In one embodiment, monomers containing a double bond and a carboxyl group include (meth) acrylic acid; Or those prepared from the reaction of an acid anhydride with a (meth) acrylate containing an alcohol group.

C ₁ as acid anhydride It may be used one or more selected from the group consisting of ~ C ₂₄ aliphatic, alicyclic, aromatic acid anhydride and (meth) acrylate, but is not necessarily limited thereto. For example, succinic anhydride, maleic anhydride, dodecyl succinic anhydride, octyl succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, pyromellitic dianhydride pyritic hydrochloride , PMDA), 3,3 ', 4,4'-oxydiphthalic dianhydride (3,3', 4,4'-oxydiphtalic dianhydride (ODPA), 3,3 ', 4,4'-benzophenonetetracarboxylic acid Dianhydrides (3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 4,4'-diphthalic acid (hexafluoroisopropylidene) anhydride (4,4'-diphtalic (hexafluoroisopropylidene) anhydride, 6FDA) At least one selected from the group consisting of benzoquinonetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, and (meth) acrylic acid anhydride can be used.

Examples of the (meth) acrylate containing an alcohol group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyisopropyl (meth) acrylate, and butanediol mono (meth) acrylate. , 4-hydroxybutyl (meth) acrylate and one or more selected from the group consisting of caprolactone (meth) acrylate can be used, but is not necessarily limited thereto.

As used herein, low molecular weight organic acid refers to an organic acid having a molecular weight of 500 or less.

In one embodiment, as a low molecular weight organic acid containing a polyvalent acid group of at least a monofunctional, di- or tri-functional, C ₁ At least one selected from the group consisting of C ₂₄ aliphatic, alicyclic and aromatic acids can be used. For example, acetic acid, formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, succinic acid, malonic acid, oxonic acid, glutaric acid, adipic acid, azelaic acid, seba At least one selected from the group consisting of citric acid, fumaric acid, aglycoric acid, citric acid, phthalic acid, isophthalic acid and terephthalic acid can be used.

In another embodiment, low molecular weight organic acids may be used instead of monoesters (half esters) of dicarboxylic acids resulting from the reaction of acid anhydrides with alcohols. Here, the acid anhydride is C ₁ At least one selected from the group consisting of C ₂₄ aliphatic, cycloaliphatic and aromatic acid anhydrides can be used, and specific types thereof are as listed above. Alcohols are polyhydric alcohols having a mono-, bi- or tri- or higher-functional, C ₁ At least one selected from the group consisting of _C12 aliphatic, cycloaliphatic, aromatic alcohols, and (meth) acrylates containing alcohol groups can be used. For example, ethylene glycol, propylene glycol, trimethylol propane, trimethylol ethane, 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol , 1,5-pentanediol, ditrimethylolpropane, triethylolpropane, glycerin, pentaerythritol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxy isopropyl ( One or more selected from the group consisting of meth) acrylate, butanediol mono (meth) acrylate, 4-hydroxybutyl (meth) acrylate and caprolactone (meth) acrylate can be used.

In one embodiment, the intermediate comprises 20 to 85 parts by weight of a monomer containing a double bond and a carboxyl group based on 100 parts by weight of solids; 10 to 65 parts by weight of a divalent metal; 5 to 85 parts by weight of low molecular weight organic acid; Solvent 10 to 90 parts by weight; And it may be prepared by mixing and reacting in a content of 5 parts by weight or less (for example, 0.01 to 5 parts by weight) of the polymerization inhibitor. In addition, the necessary catalyst may be used in an amount of 5 parts by weight or less based on 100 parts by weight of solids.

When the content of the monomer and the low molecular weight organic acid containing the double bond and the carboxyl group is too out of the above range, the monomolecular substance may increase to decrease the physical properties of the coating film or gelation when the resin is produced. If it is too far out of range, unreacted raw materials may remain, thereby reducing the physical properties of the paint.

In addition, if the content of the solvent is less than 10 parts by weight, it is difficult to prevent the rapid temperature rise, it is difficult to control the reaction temperature, if the content exceeds 90 parts by weight of the initial solvent sufficient in the binder manufacturing step (secondary reaction) to be described later May not be available. On the other hand, the polymerization inhibitor and the catalyst can be used within a range that does not adversely affect the reaction, if the content of the polymerization inhibitor exceeds 5 parts by weight may adversely affect the secondary reaction, the content of the catalyst is 5 If it exceeds the weight part, there is a possibility of discoloration.

Preferably, this step is carried out at a production temperature of 25 ~ 200 ℃. If the intermediate production temperature is less than 25 ℃ reaction rate is too slow may be a long production time, if it exceeds 200 ℃ may be discolored or radicals are formed.

The reaction product of step (a), which is an intermediate prepared according to this step, has a solid content of 10 to 90% (by weight) and an acid value of 50 to 225 mgKOH / g (based on solids). If the solids content is less than 10% wear rate and blushing may be lowered, if the solids content exceeds 90% it may be difficult to control the reaction temperature. In addition, when the acid value is less than 50 mgKOH / g may be reduced wear rate, antifouling resistance and blushing, if the acid value is more than 225 mgKOH / g crack resistance is lowered and the wear rate may be faster than necessary.

(b) Binder Preparation Step

This step (secondary reaction) is a step of finally preparing a binder for antifouling paint by copolymerizing the intermediate prepared in advance in step (a) with a radical polymerizable monomer.

The intermediate may be copolymerized with various known radically polymerizable monomers, and may also be copolymerized with silyl and tin monomers, so long as the intermediate does not adversely affect the antifouling paint.

In one embodiment, conventional acrylic monomers can be used as the monomer copolymerized with the intermediate. For example, C ₁ C ₁₂ alkyl (meth) acrylate, C _{3 C12} cycloalkyl (meth) acrylate and C ₆ - at least one element selected from the group consisting of non-cycloalkyl (meth) acrylates of C ₁₂ may be used. More specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, tertiary butyl (meth) acrylate , n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate and isobornyl (meth) acrylate One or more may be used, but is not necessarily limited thereto.

Solvents that can be used to prepare the binder according to the present invention are not particularly limited so long as they do not adversely affect the reaction. For example, aromatic hydrocarbon solvents such as toluene and xylene; Ketone solvents such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, ethyl propyl ketone, methyl isobutyl ketone and methyl aryl ketone; Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, isopropyl acetate, butyl acetate, methylcellosolve acetate, cellosolve acetate, butylcellosolve acetate, and carbitol acetate; And alcohol solvents such as n-propanol, isopropanol, n-butanol, isobutanol and tertiary butanol; may be used alone or in combination of two or more thereof. However, in the case of preparing the half ester described above, alcohol-based solvents may cause side reactions with acid anhydrides, so the use of alcohol other than the alcohol used for the purpose of reaction should be limited.

Initiators that can be used to prepare the binders according to the invention include, for example, 2,2'-azobis (2-methylbutylonitrile), 2,2'-azobisisobutylonitrile, dibenzoyl peroxide, Tertiary butyl peroxy benzoate, tertiary butyl peroxide, tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl peroxy acetate, tertiary millyl peroxy-2-ethyl hexanoate, cumyl hydroper Oxides, dicumyl peroxide, tertiary hydroperoxide, and the like, but are not necessarily limited thereto.

In one embodiment, the binder comprises 5 to 70 parts by weight of intermediate, based on 100 parts by weight of (secondary) reaction mixture; 10 to 75 parts by weight of the radical polymerizable monomer; Solvent 20 to 70 parts by weight; And it may be prepared by reacting with an amount of 1 to 20 parts by weight of the initiator.

If the content of the intermediate is less than 5 parts by weight, the wear rate, blushing and stain resistance may be lowered. If the content of the intermediate is more than 70 parts by weight, crack resistance may be reduced.

In addition, when the content of the radically polymerizable monomer exceeds the above range, the wear rate may be lowered or deepened. When the content of the solvent exceeds the above range, the reaction temperature may become difficult to control or disadvantage may occur due to the decrease of the solid content. If the content of the initiator is out of the above range, the reaction may not proceed or the impurities may increase due to excessive initiator.

[ Antifouling paint  Composition]

According to another aspect of the present invention, there is provided an antifouling coating composition comprising a binder prepared by the method as described above.

The antifouling coating composition of the present invention preferably contains 25 to 70% by weight of the binder in the total composition. If the content is less than 25% by weight there may be a problem in the coating film formation, if the content is more than 70% by weight may lower the coating performance due to low antifouling properties and high wear rate.

The antifouling coating composition of the present invention may be prepared by a conventional process by adding components commonly used in the antifouling coating composition in addition to the binder. In one embodiment, the antifouling coating composition of the present invention is one selected from the group consisting of co-binders, antifouling agents, pigments, solvents, precipitation inhibitors, antisagging agents, plasticizers, antifoaming agents and stabilizers. The above additive may be further included.

Specifically, conventional cobinders, known antifouling agents in the form of organic or inorganic compounds, pigments (such as zinc oxide, etc.), which serve to improve coating strength, control the wear rate and color, etc., various known organic and inorganic pigments Solvents commonly used in antifouling coating compositions such as titanium white, red iron oxide, organic red pigments, and talc, aliphatic, aromatics (such as xylene, toluene, etc.), ketones, esters, and ethers; In addition, conventional flow inhibitors, plasticizers (e.g., paraffin chloride, etc.), conventional antifoaming agents, and conventional stabilizers, which contribute to improving crack resistance of the antifouling coating film, may be added to the antifouling coating composition of the present invention. In addition, various resins such as acrylic resins, polyalkylvinyl ethers (vinyl ether (co) polymers), fillers, viscoelastic modifiers, storage stabilizers, and the like may additionally be included.

Preferably, the antifouling coating composition of the present invention further comprises at least one member selected from the group consisting of dissolution control components such as rosin, rosin derivatives, monocarboxylic acids and salts thereof. Therefore, it is possible to effectively control the long-term antifouling performance by controlling the dissolution rate of the antifouling agent together with the controlled wear behavior of the coating film in seawater. As rosin, rosin rosin, wood rosin, and tall oil rosin can be used as a representative, and as rosin derivatives (low melting point) disproportionated rosin, hydrogenated rosin, polymerized rosin, metal salts of rosin and rosin derivatives (copper Salts, zinc salts or magnesium salts), rosin amines, and the like, but are not necessarily limited thereto. Rosin and rosin derivatives can be used individually or in mixture of 2 or more types. As the monocarboxylic acid, fatty acids having 5 to 30 carbon atoms and synthetic fatty acids or naphthenic acid may be used, but are not necessarily limited thereto.

The content of the dissolution adjusting component may be relatively determined in view of the antifouling performance and the water resistance of the coating film. Specifically, the dissolution control component is preferably added in an amount of 0.1 to 25% by weight (solid content conversion) in the total antifouling paint composition. If the content is less than 0.1% by weight may not exhibit the initial antifouling performance complementary effect, if the content exceeds 25% by weight may weaken the hardness and water resistance of the coating film may cause the coating film collapse.

The antifouling coating composition of the present invention may be applied to any underwater transportation means, underwater structures, etc., which need to be prevented from pollution, and in particular, it can be applied to a ship hull to effectively prevent and control the attachment and growth of marine life.

Hereinafter, the present invention will be described more specifically by way of examples. However, these examples are provided only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

Example  One

[Manufacture of Binder for Antifouling Paint]

In a four-necked flask equipped with a thermometer and a cooler, 300 g of butanol, 217.7 g of zinc oxide, and 0.05 g of methylhydroquinone were added under a nitrogen atmosphere, and the temperature was raised to 80 ° C. As a monomer, a mixture of 230 g of methacrylic acid, 564.3 g of half ester (310.9 g of methyltetrahydrophthalic anhydride, 253.4 g of methoxypropanol: 85% nonvolatile matter (NV.)) And 177.3 g of naphthenic acid was mixed in 30 minutes. Dropwise uniformly over. Subsequently, isothermal holding reaction at 80 ° C. for 2 hours yielded a transparent intermediate having a solid content of 70.9% (by weight) and an acid value of 142.0 mgKOH / g (based on solid acrylic acid).

Subsequently, 300 g of butanol and 300 g of xylene were added to a four-necked flask equipped with a thermometer and a cooler under a nitrogen atmosphere in a secondary reaction, and the mixture was heated to reflux at 120 ° C. To the mixture, a mixture of 1489.3 g of intermediate obtained in the first reaction, 770 g of ethyl acrylate, 80 g of tertiary amyl peroxy hexanoate as an initiator, and 470 g of xylene was added dropwise and uniformly for 4 hours, followed by 2 hours. Reflux was maintained to obtain a resin. The obtained resin was a yellow transparent resin having a solid content of 55.3% (based on weight), Gardner viscosity (25 ° C) Z- and an acid value of 79.5 mgKOH / g (based on solid acrylic acid).

Example  2

[Manufacture of Binder for Antifouling Paint]

In a four-necked flask equipped with a thermometer and a cooler, 300 g of butanol, 217.7 g of zinc oxide, and 0.05 g of methylhydroquinone were added under a nitrogen atmosphere, and the temperature was raised to 80 ° C. As a monomer, a mixture of 230 g of methacrylic acid, 395.0 g of half ester (217.6 g of methyltetrahydrophthalic anhydride, 177.4 g of methoxypropanol: NV. 85%) and 124.1 g of naphthenic acid was added dropwise uniformly over 30 minutes. It was. Subsequently, isothermal holding reaction at 80 ° C. for 2 hours yielded a transparent intermediate having a solid content of 67.8% (by weight) and an acid value of 174.6 mgKOH / g (based on solid acrylic acid).

Subsequently, 300 g of butanol and 300 g of xylene were added to a four-necked flask equipped with a thermometer and a cooler under a nitrogen atmosphere in a secondary reaction, and the mixture was heated to reflux at 120 ° C. To this, a mixture of 1266.9 g of intermediate obtained in the first reaction, 770 g of ethyl acrylate, 120 g of tertiary amyl peroxy hexanoate and 350 g of xylene as an initiator was added dropwise and uniformly for 4 hours, followed by 2 hours. Reflux was maintained to obtain a resin. The obtained resin was a yellow transparent resin having a solid content of 55.3% (by weight), Gardner viscosity (25 ° C.) Z + and an acid value of 87.3 mgKOH / g (based on solid acrylic acid).

Example  3

[Manufacture of Binder for Antifouling Paint]

In a four-necked flask equipped with a thermometer and a cooler, 300 g of butanol, 164.2 g of zinc oxide, and 0.03 g of methylhydroquinone were added under a nitrogen atmosphere, and the temperature was raised to 80 ° C. A mixture of 173.5 g of methacrylic acid, 297.9 g of half ester (209.0 g of methyltetrahydrophthalic anhydride, 88.9 g of methoxypropanol: NV. 85%) and 93.6 g of naphthenic acid as a monomer was uniformly mixed over 30 minutes. Added dropwise. Subsequently, isothermal holding reaction at 80 ° C. for 2 hours yielded a transparent intermediate having a solid content of 63.0% (by weight) and an acid value of 174.6 mgKOH / g (based on solid acrylic acid).

Subsequently, 300 g of butanol and 300 g of xylene were added to a four-necked flask equipped with a thermometer and a cooler under a nitrogen atmosphere in a secondary reaction, and the mixture was heated to reflux at 120 ° C. Here, 1,029.2 g of intermediates obtained in the first reaction, 669 g of ethyl acrylate, 150.0 g of triisopropylsilyl acrylate, 7.5 g of 2-methoxyethyl acrylate, 80 g of tertiary amyl peroxy hexanoate as an initiator, and xylene 240 g of the mixed solution was mixed dropwise for 4 hours and then refluxed for 2 hours to obtain a resin. The obtained resin was a yellow transparent resin having a solid content of 55.3% (by weight), Gardner viscosity (25 ° C) Z, and an acid value of 73.7 mgKOH / g (based on solid acrylic acid).

Comparative example  One

[Manufacture of Binder for Antifouling Paint]

In a four-necked flask equipped with a thermometer and a cooler, 300 g of butanol and 300 g of xylene were added under a nitrogen atmosphere, and the mixture was heated to reflux at 120 ° C. Here, a mixed solution of 230 g of methacrylic acid, 770 g of ethyl acrylate, 80 g of tertiary amyl peroxy hexanoate as a initiator, and 470 g of xylene was added dropwise uniformly for 4 hours, and then refluxed for 2 hours to maintain solid content 49.3 A clear acrylic acid modified acrylic resin having a% (based on weight), Gardner viscosity (25 ° C.) BC, and an acid value of 150 mgKOH / g (based on solid acrylic acid) was obtained. Subsequently, a 4-necked flask equipped with a thermometer and a cooler, under nitrogen atmosphere, 2,150.0 g of primary reactant, 564.3 g of half ester (365.9 g of methyl tetrahydrophthalic anhydride, 198.4 g of methoxypropanol: NV. 85%), naphthenic acid 177.3 g, 217.7 g of zinc oxide, 255 g of butanol and 48.1 g of ionized water were added thereto, and the temperature was raised to 80 ° C., after 10 hours, to confirm that the appearance of the resin was transparent. The reaction was terminated to obtain a resin. The obtained resin was a yellow transparent resin having a solid content of 55.3% (based on weight), Gardner viscosity (25 ° C) Z- and an acid value of 79.5 mgKOH / g (based on solid acrylic acid).

Comparative example  2

[Manufacture of Binder for Antifouling Paint]

In a four-necked flask equipped with a thermometer and a cooler, 300 g of butanol and 300 g of xylene were added under a nitrogen atmosphere, and the mixture was heated to reflux at 120 ° C. Here, a mixture of 230 g of methacrylic acid, 770 g of ethyl acrylate, 120 g of tertiary amyl peroxy hexanoate and 350 g of xylene as an initiator was added dropwise to the mixture for 4 hours, and then refluxed for 2 hours to maintain a solid content of 52.6%. A clear acrylic acid-modified acrylic resin having a Gardner viscosity (25 ° C.) A1-A (based on weight) and an acid value of 150 mgKOH / g (based on solid acrylic acid) was obtained. Then, a four-necked flask equipped with a thermometer and a cooler was subjected to 2,070.0 g of a primary reactant, 395.0 g of a half ester (217.6 g of methyltetrahydrophthalic anhydride, 177.4 g of methoxypropanol: NV. 85%) under a nitrogen atmosphere, and naphthenic acid. 124.1 g, 217.7 g of zinc oxide, 255 g of butanol, and 48.1 g of ionized water were added thereto, and the temperature was raised to 80 ° C .. After 30 hours, the resin appearance was transparent. The obtained resin was a yellow transparent resin having a solid content of 55.3% (by weight), Gardner viscosity (25 ° C.) Z + and an acid value of 87.2 mgKOH / g (based on solid acrylic acid).

Comparative example  3

[Manufacture of Binder for Antifouling Paint]

In a four-necked flask equipped with a thermometer and a cooler, 300 g of butanol and 300 g of xylene were added under a nitrogen atmosphere, and the mixture was heated to reflux at 120 ° C. Here, 173.5 g of methacrylic acid, 669 g of ethyl acrylate, 150.0 g of triisopropylsilyl acrylate, 7.5 g of 2-methoxyethyl acrylate, 80 g of tertiary amyl peroxy hexanoate as an initiator, and 240 g of xylene were respectively mixed. A mixed solution was added dropwise evenly for 4 hours and then refluxed for 2 hours to provide a clear acrylic acid-modified acrylic resin having a solid content of 55.2% (by weight), Gardner viscosity (25 ° C) A- and an acid value of 150 mgKOH / g (based on solid acrylic acid). Obtained. Subsequently, a 4-necked flask equipped with a thermometer and a cooler was subjected to 1,920.0 g of a primary reactant, 297.9 g of a half ester (209.0 g of methyltetrahydrophthalic anhydride, 88.9 g of methoxypropanol: NV. 85%) under a nitrogen atmosphere, and naphthenic acid. 93.6 g, zinc oxide 164.2, butanol 265 g, and ionized water 36.3 g were added thereto, and the temperature was raised to 80 ° C. and maintained for 35 hours to confirm that the appearance of the resin was transparent. The obtained resin was a yellow transparent resin having a solid content of 55.3% (by weight), Gardner viscosity (25 ° C) Z, and an acid value of 73.7 mgKOH / g (based on solid acrylic acid).

[Table 2] Binder Formulation and Manufacturing Time

1) MAA: methacrylic acid

2) EA: ethyl acrylate

3) TIPX: triisopropylsilyl acrylate

4) 2-MEA: 2-methoxyethyl acrylate

5) H / E: half ester (methyltetrahydrophthalic anhydride + methoxypropanol, solid content (by weight): 85%)

6) N / A: naphthenic acid

7) ZnO: Zinc Oxide

8) MeHQ: Methylhydroquinone

9) TAPO: tertyl amyl peroxy 2-methylhexanoate

10) Acid Value: Solid Acrylic Acid Standard

Example  4 to 6 and Comparative example  4 to 6

[Production of antifouling coating composition]

Using the binders prepared according to Examples 1 to 3 and Comparative Examples 1 to 3 to prepare an antifouling coating composition in the formulation shown in Table 3.

[Table 3] Antifouling paint formulation

Rosin: Gum Rosin [Jianxi sino native products]

2) Plasticizer: Paraffin plastoil 152 [Handy chemical corporation]

3) Bengala: Iron Oxide Red 308 [Woo shin pigment co ,. Ltd.]

4) Titanium Bag: TIPAQUE CR-9 [Ishihara Sangyo Kaisha, Ltd.]

5) Talc: NA-400 [Young woo chemical co, .Ltd.]

6) Copper salt pyrithione: Copper Omadine Powder [Arch UK biocide Ltd]

7) Aliphatic Amide Wax Paste: Monoral 5500M [HS Chem.]

8) Copper Oxide: Red Copp 97N Premium [American Chemet]

9) Xylene: Xylene [SK corporation]

The physical properties of the prepared antifouling paints were evaluated in the following manners, and the results are shown in Table 4 below.

Paint solids

1. Test conditions: About 3.0g sampling of manufactured paint, 150 ℃ × 24 hours

2. Solid content (%): {weight after heating / weight before heating} * 100

Paint viscosity

Test condition: 25 ℃, measured with Kreb's Unit

Anti-wood pressure  exam

Specimen: 100 × 300 × 3 (mm) steel plate

2. Specimen treatment: sand blasting → epoxy-based anticorrosive paint 150㎛ → epoxy binder paint 100㎛ (1 day drying at room temperature (20 ℃) after coating each paint)

3. Antifouling paint: 1 week drying at room temperature (20 ℃) after 300㎛ coating

4. Test condition: Strain measurement after 40 minutes of pressing at 50 kg _f / ㎠ using 20 × 20 × 20 (mm) wooden piece

5. Strain (%): 100-{(film thickness after pressure / film thickness before pressure) * 100}

6. Evaluation: According to the criteria below

* Strain Evaluation Criteria

5: less than 3% strain

4: more than 3% of strain less than 5%

3: 5% or more strain less than 7%

2: strain 7% or more to less than 10%

1: more than 10% strain

crack  Resistance test

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

2. Specimen treatment: sand blasting → epoxy-based anticorrosive paint 150㎛ → epoxy binder paint 100㎛ (1 day drying at room temperature (20 ℃) after coating each paint)

3. Antifouling paint: 1 week at room temperature (20 ℃) after 600㎛ coating

4. Test conditions: 24 hours immersion in 23 ℃ seawater → 24 hours outdoor drying-30 repetitions

5. Evaluation: According to the criteria below

* Crack Resistance Evaluation Criteria

5: no cracks or cosmetic defects

4: Cracks occur in less than 5% of the total area of the test specimen

3: Cracks occur at more than 5% and less than 20% of the total area of the test specimen

2: Cracks occur from more than 20% to less than 50% of the total area of the test specimen

1: Cracks occur at more than 50% and less than 70% of the total area of the test specimen

0: Cracks occur in more than 70% of the total area of the test specimen

Antifouling performance  exam

Specimen: 550 × 150 × 2 (mm) steel sheet

2. Specimen treatment: sand blasting → epoxy-based anticorrosive paint 200㎛ → epoxy binder paint 100㎛ (1 day drying at room temperature (20 ℃) after coating each paint)

3. Antifouling paint: 1 week drying at room temperature (20 ℃) after 300㎛ coating

4. Test conditions: Raft type test rafts installed in Ulsan Defense Port (East Coast) and Geojedo offshore (South Coast). Submerged 1m below sea level.-Observed every 3 months.-18 months.

5. Evaluation: According to the criteria below

* Antifouling performance evaluation standard

5: No attachment of marine organisms (non-contaminated)

4: thin slime layer observed

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

2: The plant contamination area is more than 20% and less than 50% of the effective area of the specimen

1: Plant contamination is greater than 50% and less than 100% of the effective area of the specimen

X: Animal Contamination

Wear rate measurement

Specimen: 150 × 70 × 1 (mm) stainless steel sheet

2. Specimen treatment: Epoxy type anticorrosive paint 50㎛ → Epoxy binder paint 50㎛

3. Antifouling paint: 1 week drying at room temperature (20 ℃) after coating 100㎛

4. Test conditions: rotating drum (600mm × 300mm), speed 25knot-1 month cycle observation-12 months measurement

[Table 4] Antifouling paint properties

As shown in Table 2 and Table 4, in the case of the production example was much shorter than the comparative example, but showed a viscosity, coating strength, crack resistance, antifouling performance and wear performance equivalent to the comparative example, the solid content than the comparative example Even higher.

Claims (11)

(a) reacting a monomer containing a double bond and a carboxyl group, or a low molecular weight organic acid or both with a divalent metal to prepare an intermediate represented by one of the following Chemical Formulas 1 to 3; And
(b) comprising the step of copolymerizing the intermediate and the radical polymerizable monomer, a method for producing a binder for antifouling paint.
[Formula 1]

(2)

(3)

(Wherein R ¹ , R ³ and R ⁴ each independently represent H or CH ₃ ; R ² , R ⁵ and R ⁶ each independently represent an organic group; M represents a divalent metal.) The monomer of claim 1, wherein the monomer containing a double bond and a carboxyl group is selected from (meth) acrylic acid; Or (meth) acrylate containing an alcohol group and a monomer containing an acid anhydride. The antifouling coating binder according to claim 1, wherein the low molecular weight organic acid contains an acid group having a consistent ability or higher, and is at least one member selected from the group consisting of C ₁ to C ₂₄ aliphatic, alicyclic and aromatic acids. Manufacturing method. The method for producing a binder for antifouling paint according to claim 1, wherein the low molecular weight organic acid is a monoester (half ester) of dicarboxylic acid prepared from the reaction of an acid anhydride and an alcohol. The method of claim 1, based on 100 parts by weight of solids
20 to 85 parts by weight of a monomer containing a double bond and a carboxyl group;
10 to 65 parts by weight of a divalent metal;
5 to 85 parts by weight of low molecular weight organic acid;
Solvent 10 to 90 parts by weight; And
A method for producing a binder for an antifouling paint, comprising reacting a mixture of 0.01 to 5 parts by weight of a polymerization inhibitor. The method of claim 1, wherein the step (a) is carried out at 25 ~ 200 ℃. The method for preparing a binder for antifouling paint according to claim 1, wherein an intermediate having a solid content (weight basis) of 10 to 90% and an acid value (solid content basis) of 50 to 225 mgKOH / g is prepared. The method for producing a binder for antifouling paint according to claim 1, wherein the radical polymerizable monomer is a nonfunctional acrylic monomer. The method of claim 1, wherein based on 100 parts by weight of the reaction mixture of step (b)
5 to 70 parts by weight of the intermediate;
10 to 75 parts by weight of the radical polymerizable monomer;
Solvent 20 to 70 parts by weight; And
A method for producing a binder for an antifouling paint, comprising reacting 1 to 20 parts by weight of an initiator to produce a binder. A binder for antifouling paint prepared according to any one of claims 1 to 9. An antifouling coating composition comprising the binder according to claim 10.