KR101755106B1 - Resin for antifouling paint composition having excellent anti-foul performance, antifouling paint composition comprising the same and method for preparing the antifouling paint composition - Google Patents

Abstract

The present invention relates to a composition comprising a first monomer containing a double bond as a polymerization unit; And a second monomer containing a carboxylic acid group and a double bond, wherein the number of the elements in the linear chain connecting the double bond and the carboxylic acid group in the second monomer is greater than the number of double bonds in the first monomer (Long Chain Acid) which is 4 or more than the number of elements in the straight chain connected to the resin, and which can control the abrasion speed of the antifouling paint and improve the frictional resistance and crack resistance, To an antifouling paint composition and a method for producing the same.

Description

TECHNICAL FIELD The present invention relates to an antifouling paint composition having excellent antifouling properties, an antifouling paint composition containing the antifouling paint composition and an antifouling paint composition having excellent antifouling properties,

The present invention relates to a resin for an antifouling paint excellent in antifouling property, an antifouling paint composition comprising the same, and a process for producing the same.

The coating composition to which the antifouling resin is applied is intended to prevent or control adhesion and growth of marine organisms causing surface contamination of the seawater-deposited coating film. When various marine organisms are adhered to the surface of the film, the frictional force between the surface of the coating and the seawater during operation of the vessel increases, which can significantly increase the fuel cost, which is a significant portion of the operating expense. The antifouling paint is a paint for removing such adherence to reduce the coefficient of friction between water and ship during operation.

The antifouling paints have an insoluble type using a binder that does not dissolve in water and a water-soluble type that uses a water-soluble binder. The insoluble type is an antifouling paint prepared by adding a large amount of an antifouling agent such as copper oxyhydroxide to an old-fashion antifouling paint using water-insoluble vinyl, a chlorinated rubber resin or the like. In the state that the resin- The antifouling agent such as copper oxide and the like is gradually diffused into seawater to exhibit the antifouling performance. The water-soluble type is a paint used with an antifouling agent by mixing water-soluble resin and insoluble resin such as rosin. Antifouling agent contained in the coating film while the resin is dissolved in water exhibits the antifouling performance as the seawater. The water-soluble type has a longer antifouling performance than the insoluble type, but the time period during which the coating film does not melt uniformly and the antifouling performance is exhibited is limited to 3 years or less.

The antifouling paint widely used at present is a method in which an insoluble resin is mixed with seawater to hydrolyze and gradually dissolves into water-soluble and dissolves the antifouling agent such as copper oxide to release the antifouling performance. Since the rate of dissolution in seawater is controlled uniformly compared to existing water-soluble types, long-term antifouling performance can be achieved.

Antifouling paints can be classified into tin type and non-tin type depending on whether there is tin or not. Non-tin type can be divided into metal type and silyl type. The tin type is a structure in which tributyltin oxide is chemically bonded to the acrylic main chain, and is hydrolyzed in an alkali of pH 8 or higher to become a copolymer of acrylic acid and slowly dissolves in weakly alkaline sea water. Especially hydrolyzed tributyltin has its own antifouling property, so it has the merit of magnetic wear characteristics and self - repellant. However, due to tributyltin poisoning, malformations such as fish malformation and female males have been highlighted and their use has been regulated since 2003,

The non-ferrous metal type has a structure similar to that of the tin type, and is formed by bonding Zn or Cu to acrylic acid or an acid compound and is dissolved in seawater due to hydrolysis. Since non-ferrous metal type does not have its own antifouling property, it merely carries out the function of self-abrasion control by hydrolysis and adds oily / antifouling agent to impart flame proof. In addition, the silyl type, which has recently been attracting attention, has a high chemical stability and can be used in various antifouling agents, and has a more stable wear rate than the non-sapphire metal type. However, since the silyl type acrylic monomer is expensive, the overall raw material cost is increased, and the abrasion rate at the time of anchorage is low, so that the antifouling property may not be sufficient.

In recent years, in addition to the ability to prevent or control the attachment and growth of marine organisms that cause pollution, they have long-term functions, reduced fuel cost by reducing frictional resistance with seawater, volatile organic compound (VOC) content And other functions are added to the antifouling paint.

JP-A-1990-196869 discloses a hydrolyzable copolymer composed of trimethylsilyl (meth) acrylate and an unsaturated monomer. Trimethylsilyl (meth) acrylate has been reported to have a degree of hydrolysis of about 70% as compared to conventional tin-based binders. This is because the metal ester structure is relatively covalent to silicon in comparison with tin, It seems to be because of Therefore, the content of hydrolyzed trimethylsilyl (meth) acrylate must be higher than that of other antifouling coating compositions. However, the trimethylsilyl (meth) acrylate monomer is relatively expensive in terms of cost and has a problem that the crack resistance of the binder becomes poor when the content is higher than necessary. Further, when a material having a small number of carbon atoms of an alkyl group bonded to silicon is applied to improve the hydrolysis property, there is a problem that the long term storage property is poor.

Korean Patent Laid-Open Publication No. 1997-7004840 discloses a method of mixing a plastic (meth) acrylate copolymer to solve the problem of a copolymer composed of a trimethylsilyl (meth) acrylate monomer. However, in this case, there is a problem that as the nonhydrolyzable binder remains after long-term wear in seawater, the wear rate gradually decreases.

Korean Patent Laid-Open Publication No. 2013-0093840 discloses a process for producing an organic acid containing a carboxylic acid group and an amine group by a radical reaction of a monomer containing a divalent metal and a double bond and a carboxylic acid group and a double bond and an alkyl group A resin for an antifouling paint prepared by a condensation reaction with an acrylic resin, and an antifouling paint composition containing the same. In this case, application of an organic acid containing a carboxylic acid group and an amine group has physical properties improved in discoloration resistance and crack resistance, but it is insufficient to exhibit low viscosity and high specific gravity.

The present invention includes a copolymer comprising a first monomer containing a double bond and a second monomer containing a carboxylic acid group and a double bond as a polymerization unit, wherein the second monomer is a copolymer of a linear monomer having a double bond and a carboxylic acid group (Long Chain Acid) of which the number is four or more than the number of the elements in the straight chain connected to the double bond of the first monomer, the abrasion rate of the antifouling paint can be controlled, and the frictional resistance and crack resistance can be improved An antifouling paint composition containing the same, and a process for producing the same.

The resin for an antifouling paint of the present invention comprises a copolymer comprising a first monomer containing a double bond and a second monomer containing a carboxylic acid group and a double bond as a polymerization unit and is characterized in that a double bond of the second monomer and a carboxylic acid group The number of the elements in the linear chain connected to the double bond of the first monomer is four or more than the number of the elements in the linear chain connected to the double bond of the first monomer.

The antifouling paint composition of the present invention comprises the resin for the antifouling paint.

The method for producing an antifouling paint composition of the present invention comprises: a first monomer containing a polymerizable double bond; And a second monomer containing a carboxylic acid group and a double bond to form a radical reaction product; And mixing the radical reaction product with a divalent metal and an organic acid, wherein the number of the elements in the linear chain connecting the double bond and the carboxyl group of the second monomer to the radical It is more than 4 more than the number of chain elements.

According to the present invention, it is possible to provide an antifouling paint composition capable of controlling the wear rate of the antifouling paint and improving the frictional resistance and crack resistance.

Fig. 1 shows a comparison between the conventional antifouling paint binder and the antifouling paint binder of the present invention.

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

The resin for an antifouling paint of the present invention comprises a first monomer containing one double bond as a polymerization unit; And a second monomer containing one carboxylic acid group and one double bond, wherein the number of straight-chain elements connecting the double bond of the second monomer and the carboxylic acid group is greater than the number of the first monomer Wherein the number of the linear elements connected to the double bond of the monomer is 4 or more.

The first monomer may be represented by the following general formula (1).

[Chemical Formula 1]

In this formula,

-X- is any one selected from the group consisting of a single bond, a C ₁ to C ₆₀ aliphatic group, a C ₃ to C ₆₀ alicyclic group, a heteroaliphatic ring group, a heteroaromatic ring group, and a C ₆ to C ₆₀ aromatic group Or a straight chain linkage of two or more of them.

More specifically, -X- is _{^{- (CR 1 R 2) a}} '-, - (CR 3 = CR 4) a''-, - (CO) a''' -, - (O) b -, - (NR ⁵ ) _c -, and - (S) _d -, or wherein R, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are Each independently represent a hydrogen, aliphatic, alicyclic or aromatic hydrocarbon group,

a '', a '' ', b, c, and d each represents an integer of 0 or more and represents the sum of the number of each connector contained in -X-,

(the number of carbon atoms on the short side between the neighboring functional groups of the bivalent aliphatic ring and the respective carbons bonded to each other + 1) is n = a '+ (a' '+ 1) + a' '' + b + c + d +

The second monomer may be represented by the following formula (2).

(2)

In this formula,

-Y- is any one selected from the group consisting of a single bond, a C ₁ to C ₆₀ aliphatic group, a C ₃ to C ₆₀ alicyclic group, a heteroaliphatic ring group, a heteroaromatic ring group, and a C ₆ to C ₆₀ aromatic group Or a straight chain linkage of two or more of them.

More specifically, -Y- is _{^{- (CR 6 R 7) e}} '-, - (CR 8 = CR 9) e''-, - (CO) e''' -, - (O) f -, - (NR ¹⁰ ) _g -, and - (S) _h -, wherein Q, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently selected from the group consisting of Each independently represent a hydrogen, aliphatic, alicyclic or aromatic hydrocarbon group,

e ', e' ', f, g, and h are integers of 0 or more and represent the sum of the number of each connector included in -Y-,

(the number of carbon atoms on the short side between the neighboring functional groups of the bivalent aliphatic ring and the respective carbons) + m + e + 1 + e + f + g + h +

In Formula 1 and Formula 2, the heteroaliphatic ring or heteroaromatic may be a C ₅ to C ₆₀ heteroaliphatic ring or heteroaromatic containing at least one heteroatom selected from N, O and S.

The aliphatic hydrocarbon group may be a C ₅ to C ₉₀ alkyl group, the alicyclic hydrocarbon group may be a C ₅ to C ₉₀ cycloalkyl group, and the aromatic group may be a C ₆ to C ₉₀ aromatic group.

FIG. 1 shows a comparison between the structure of a conventional binder for an antifouling paint and a binder (copolymer) for an antifouling paint of the present invention. When a copolymer produced by the present invention is applied to a coating material, a metal It is possible to provide an antifouling paint composition having an improved antifouling performance because a resin structure is formed in which the relative length of the ester (the part of the acrylic resin with which the carboxylic acid, zinc and the organic acid are bonded) is longer than the peripheral side chains and relatively easier to hydrolyze have.

When the side chain of the metal ester is used as a hydrophilic component or a minor component, it is possible to secure a reduction in frictional resistance and an improvement in crack resistance. When the hydrophilic component is applied, the hydrophilic component can be arranged more easily in the outward direction of the resin, so that the frictional resistance can be reduced. If the hydrophobic component is applied, the flexibility of the resin is increased and the crack resistance can be improved. Therefore, an antifouling paint composition improved in friction resistance and crack resistance can be provided.

The resin for an antifouling paint of the present invention An aliphatic organic acid having 1 to 24 carbon atoms, an alicyclic organic acid having 3 to 24 carbon atoms, an aromatic organic acid having 6 to 24 carbon atoms, and a half ester resulting from the reaction of an acid anhydride with an alcohol. have.

The resin for an antifouling paint of the present invention may further comprise at least one divalent metal ion selected from the group consisting of Zn ^{2 +} , Cu ^{2 +} , Mn ^{2 +} and Co ^{2 +} .

According to another aspect of the present invention, there is provided an antifouling paint composition comprising the resin for an antifouling paint.

Although not particularly limited, the antifouling paint composition of the present invention may comprise, based on 100% by weight of the total composition, a first monomer containing one double bond as a polymerization unit and a second monomer containing one carboxylic acid group and one double bond 10 to 50% by weight of a copolymer comprising a monomer; 10 to 60% by weight of antifouling; 0.1 to 20% by weight of an antifouling agent elution regulator; And 15 to 60% by weight of a solvent, wherein the number of straight-chain elements connecting the double bond of the second monomer and the carboxylic acid group is 4 or more more than the number of straight-chain elements connected to the double bond of the first monomer will be.

Although not particularly limited, the copolymer is preferably a copolymer having a carboxylic acid group and a double bond-containing monomer, wherein the number of straight-chain elements connecting the double bond and the carboxylic acid group is the number of straight-chain elements connected to the double bond of the first monomer But not more than one to three more monomers. The content of the copolymer may be 10 to 50% by weight, for example 15 to 40% by weight, for example 20 to 30% by weight, based on 100% by weight of the composition.

The antifouling paint composition of the present invention uses the copolymer as a binder component, whereby the resin is hydrolyzed in water, and the antifouling component contained in the coating film exits the seawater and exhibits antifouling performance. The antifouling paint composition of the present invention may contain various additives described below, including the resin for the antifouling paint of the present invention, as a binder component. In particular, it may include an antifouling agent and an antifouling agent elution controlling agent capable of controlling the long-term antifouling performance by controlling the antifouling agent elution.

For example, the antifouling agent is selected from the group consisting of copper oxide, 4,5-dichloro-2-propylisothiazol-3 (2H) -one, 4,5- (3,4-dichlorophenyl) -N, N-dimethylurea, zinc ethylene-1,2-bis (dithiocarbamate) -1,2-bis (dithiocarbamate), Zinc pyrithione, copper pyrithione, 2-methylthio-4-t-butylamino-6-cyclopropylamino- 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, triphenylboron pyridine, and 2- (P- chlorophenyl) (P-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethyl pyrrole.

The antifouling agent content may be 10 to 60% by weight, for example 15 to 50% by weight, for example 15 to 45% by weight, based on 100% by weight of the total composition.

The antifouling agent elution controlling agent of the present invention has a role of controlling the elution rate of the antifouling agent together with the controlled abrasion behavior of the coating film in seawater. As such components, those generally selected from the group consisting of rosin, rosin derivatives, monocarboxylic acids and salts thereof can be exemplified. Rosin rosin, wood rosin and tall oil rosin are representative examples of rosin. Examples of the rosin derivatives include disodium rosin (low melting point), hydrogenated rosin, polymerized rosin, metal salts (copper salts, zinc salts or magnesium salts) of rosin and rosin derivatives, and rosin amines. The rosin and rosin derivatives may be used independently or in combination of one or more. Examples of the monocarboxylic acid include fatty acids and synthetic fatty acids having 5 to 30 carbon atoms, and naphthenic acid.

It is preferable that the antifouling agent elution controlling agent is contained in an amount of 0.1 to 20% by weight (as solid content), for example, 0.5 to 15% by weight, for example, 1 to 10% by weight based on the total weight of the antifouling paint composition. The antifouling performance and the water-resisting performance may be deteriorated.

The solvent contained in the antifouling paint composition of the present invention is not particularly limited so long as it does not adversely affect the reaction. Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, Ketone solvents such as methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone and methyl aryl ketone; ketone solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, methyl cellosolve acetate, cellosolve acetate, Acetate, and carbitol acetate, or alcoholic solvents such as n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol. More specifically, toluene or xylene can be used.

In the antifouling paint composition of the present invention, the solvent may be contained in an amount of, for example, 15 to 60% by weight based on 100% by weight of the total composition. If the content of the solvent in the composition is excessively low, the viscosity may increase and the workability may deteriorate. On the other hand, if the content is too high, the solids content and SVR (solid volume ratio) have.

The antifouling paint composition of the present invention may further comprise at least one additive selected from a pigment, a plasticizer, an anti-flow agent, an anti-settling agent and an antifoaming agent. For example, a pigment component such as zinc oxide that acts to improve the film strength, control and coloration of the wear rate, an anti-sagging agent, an anti-settling agent, an antifouling paint, Various resins and defoaming agents such as plasticizers, acrylic resins and polyalkyl vinyl ethers (vinyl ether (co) polymers) can be described. In addition, various known organic and inorganic pigments (for example, titanium white, iron oxide red, organic red pigments and talc) can be used in the antifouling paint composition. Various solvents commonly used in antifouling paint compositions such as aliphatic, aromatic (for example, xylene, toluene, etc.), ketone, ester and ether solvents can be added.

The method for producing an antifouling paint composition of the present invention comprises: a first monomer containing one polymerizable double bond; And a second monomer containing one carboxylic acid group and one double bond, to form a radical reaction product; And mixing the radical reaction product with a divalent metal and an organic acid, wherein the number of the elements in the linear chain connecting the double bond and the carboxyl group of the second monomer to the radical And the number of the elements on the chain is 4 or more.

The process for producing an antifouling paint composition of the present invention can be classified into a first reaction and a second reaction. The product of the first reaction is carried out by a conventional radical reaction, and the second reaction product is prepared by the condensation reaction of the first reactant, the divalent metal and the organic acid.

The solvent which can be used in the first reaction is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include 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, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate and carbitol acetate; Or alcohol solvents such as n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol. However, when acid anhydrides are used in the reaction, alcohol solvents may cause side reactions with acid anhydrides. Therefore, the use of other alcohol groups other than those used for reaction purposes should be restricted.

The primary reactant (radical reaction product)

The first reactant according to the present invention is produced by a radical reaction between a monomer containing a double bond and an alkyl group (hereinafter referred to as a first monomer) and a monomer containing a double bond and a carboxylic acid group (hereinafter referred to as a second monomer) Respectively. The second monomer containing a double bond and a carboxylic acid group, if it contains an unsaturated hydrocarbon and a carboxylic acid group, is not affected by its structure.

In one embodiment, the first monomer comprising the double bond and the alkyl group may be represented by the formula (1).

In another embodiment, the second monomer may be Undecylenic acid represented by Formula 3, wherein R = H, n = 8.

(3)

In another embodiment, the second monomer may be a maleic anhydride modified acrylic acid represented by formula (4), wherein Y is - (CO) _{e ''} -, - (O ^{_{) f -, - (CR 6}} R 7) e '-, - (CR 6 R 7) e' -, - (O) f -, - (CO) e '''-, and - (CR ⁸ = CR ⁹⁾ _{e ''} - it is a linear combination of, where Q = H, and ^{R 6 = R 7 = R 8} = R 9 = H, wherein e '''= 2, f = 2, e' = 2, e ''= 1, so m = 2 + 2 + 2 + (1 + 1) = 8.

[Chemical Formula 4]

In another embodiment, the second monomer may be a hexahydrophthalic anhydride modified acrylic acid represented by formula (5) wherein Y is - (CO) _{e '''} -, _{- (O) f -, -} (CR 6 R 7) e '-, - (CR 6 R 7) e' -, - (O) f -, - (CO) e '''- and cycloaliphatic of C ₆ the linear combination of the group in which and ^{Q = H, R 6 = R} 7 = H, wherein e '''= 2, f = 2, e' = 2, and "respectively combined with the functional groups neighboring the above aliphatic ring The number of carbon atoms on the short side between carbons + 1 = 3 ". Therefore, m = 2 + 2 + 2 + (2 + 1) = 9.

[Chemical Formula 5]

In another embodiment, the second monomer may be a hexahydrophthalic anhydride modified methacrylic acid represented by formula (6) wherein Y is - (CO) _{e ''' -, [- (O) f} -, - (CR 6 R 7) e '-, - (CR 6 R 7) e' -] * 3, - (O) f -, - (CO) e ''' - and a linear combination of the alicyclic C _6, where Q = CH _3, R is a ⁶ = R ⁷ = H, wherein e '''= 2, f = (1 * 3) + 1 = 4, e' = 2 + 3 = 6, and "the carbon number on the short side between the adjacent functional group of the aliphatic ring and the carbon which bonds with each other + 1 = 3 ". Therefore, n = 2 + 4 + 6 + .

 [Chemical Formula 6]

The primary reactant can be prepared by a conventional radical polymerization method. The solid content of the second monomer may be 5 wt% to 90 wt% based on the solid content of the radical reaction product. When the second monomer is less than 5 wt%, the wear rate is not increased, And if it exceeds 90% by weight, the wear rate will be excessively high and it will be difficult to guarantee a full performance warranty.

The radical reaction product may have a solids content of 10 to 90% by weight based on the total weight, and an acid value of the solid content of 50 to 225 mg KOH / g. When the solid content is less than 10% by weight, the abrasion resistance and discoloration resistance are deteriorated. When the solid content is more than 90% by weight, the reaction temperature is not controlled. When the acid value is less than 50 mg KOH / g, the abrasion rate, antifouling property and discoloration resistance are lowered. On the other hand, when the acid value is more than 225 mg KOH / g, crack resistance is lowered and the abrasion rate is higher than necessary .

Bivalent metal

The divalent metal used in the production of the antifouling paint composition of the present invention has a role of generating a bond which enables the coating film to be hydrolyzed by seawater to wear, preferably Zn ^{2 +} , Cu ^{2 +} , Mn ^{2 +} and Co ^{2 +,} and the like, but is not limited thereto.

Organic acid

The organic acid used in the present invention refers to an organic acid having a molecular weight of 1,000 or less. The term "molecular weight" as used herein means a number average molecular weight. As containing one functional, bifunctional or polyhydric least three functional acid groups with an organic acid, selected from the group consisting of an aromatic acid of the C ₁ to C ₂₄ aliphatic acids, C ₃ to C ₂₄ aliphatic acid and a C ₆ to C ₂₄ of the May be used. For example, there may be mentioned acetic acid, formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, succinic acid, malonic acid, oxanic acid, glutaric acid, adipic acid, At least one selected from the group consisting of citric acid, fumaric acid, iglycolic acid, citric acid, phthalic acid, isophthalic acid and terephthalic acid can be used.

Alternatively, the half ester generated from the reaction of an acid anhydride with an alcohol in the organic acid used in the present invention may be used instead. The acid anhydride may be at least one selected from the group consisting of C ₁ to C ₂₄ aliphatic, alicyclic, and aromatic acid anhydrides, and the acid anhydride monomer may be at least one selected from the group consisting of C ₁ to C ₂₄ aliphatic, alicyclic or aromatic Acid anhydrides and preferably anhydrides such as succinic anhydride, maleic anhydride, dodecylsuccinic anhydride, octylsuccinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, pyromellitic anhydride, (PMDA), 3,3 ', 4,4-oxydiphthalic dianhydride (ODPA), 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA), 4,4 ' (6FDA), benzoquinonetetracarboxylic acid dianhydride, ethylene tetracarboxylic acid dianhydride and (meth) acrylic acid anhydride, in the presence of at least one selected from the group consisting of diphthalic acid (hexafluoroisopropylidene) anhydride It is at least one that is. Examples of the alcohol include polyhydric alcohols having a monofunctional, bifunctional or trifunctional or higher functional group and are selected from the group consisting of C ₁ to C ₁₂ aliphatic alcohols, C ₃ to C ₁₂ alicyclic alcohols, and C ₆ to C ₁₂ aromatic alcohols One or more species can be used. Examples of the solvent include ethylene glycol, propylene glycol, trimethylol propane, trimethylol ethane, 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,3-butylene glycol, (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyisopropyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, butanediol mono (meth) acrylate, 4-hydroxybutyl (meth) acrylate and caprolactone (meth) acrylate.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.

[Example]

Synthesis Example 1: Oligomer 1 (Second monomer)

221 g of 2-hydroxyethyl acrylate, 0.175 g of butylated hydroxytoluene and 279 g of hexahydrophthalic anhydride were charged into a four-necked flask equipped with a stirrer, a thermometer and a condenser, and the mixture was heated to 90 DEG C and maintained for 6 hours. A solid content of 100%, an acid value of 203 mg KOH / g, a Gardner viscosity (25 캜) U, and a light brown transparent oligomer 1.

Synthesis Example 2: Synthesis of oligomer 2 (second monomer)

A thermometer and a condenser was charged with 312 g of 2-oxepanone 2- [2-methyl (1-oxo-2-propanyl) oxy] ethyl ester, 0.175 g of butylated hydroxytoluene, 0.1 g of hexahydrophthalic anhydride And the temperature was raised to 90 占 폚 and maintained for 6 hours. A solid content of 100%, an acid value of 137 mg KOH / g, a Gardner viscosity (25 DEG C) S, and a light brown transparent oligomer 2 were obtained.

Synthesis Example 3: Oligomer 3 (Second monomer)

300 g of polyethylene glycol (n = 3) monomethacrylate, 0.175 g of butylated hydroxytoluene and 200 g of hexahydrophthalic anhydride were charged into a four-necked flask equipped with a stirrer, a thermometer and a condenser, Respectively. A solid content of 100%, an acid value of 146 mg KOH / g, a Gardner viscosity (25 캜) V, and a light brown transparent oligomer 3.

Synthesis Example 4: Oligomer 4 (Second monomer)

398 g of propylene glycol polybutylene glycol (n = 6) monomethacrylate, 0.175 g of butylated hydroxytoluene and 102 g of hexahydrophthalic anhydride were charged into a four-necked flask equipped with a stirrer, a thermometer and a condenser, And maintained for 6 hours. A solid content of 100%, an acid value of 146 mg KOH / g, a Gardner viscosity (25 DEG C) V, and a light brown transparent oligomer 4 were obtained.

Synthesis Example 5: Oligomer 5 (Second monomer)

289 g of polyethylene glycol (n = 3) monomethacrylate, 0.175 g of butylated hydroxytoluene and 211 g of methylhexahydrophthalic anhydride were charged into a four-necked flask equipped with a stirrer, a thermometer and a condenser, Respectively. A transparent oligomer 5 having a solid content of 100%, an acid value of 141 mg KOH / g, a Gardner viscosity (25 ° C) T to U, and a light brown color.

Synthesis Example 6: Binder (A) (Example 1)

A thermometer and a condenser, 92 g of butanol and 92 g of xylene were charged in a nitrogen atmosphere, and the mixture was heated to 120 ° C and refluxed. A mixed solution prepared by mixing 151 g of undecylenic acid, 61 g of methyl methacrylate, 94 g of ethyl acrylate, 15 g of tertiary amyl peroxyhexanoate as an initiator and 107 g of xylene was uniformly added dropwise over 4 hours, Lt; / RTI > The reaction mixture was then cooled to 60 ° C and subjected to an interim test (solid content: 51.9%, acid value: 150 mg KOH / g). 181 g of naphthenic acid, 67 g of zinc oxide, 132 g of xylene and 7 g of ionized water were charged, and the temperature was raised to 100 캜 at the reflux temperature. The mixture was refluxed at 100 DEG C for 5 hours to obtain a transparent resin binder (A) having a solid content of 55.1%, a Gardner viscosity (25 DEG C) Z, and a brown color.

Synthesis Example 7: Binder (B) (Example 2)

A thermometer and a condenser, 116 g of butanol and 116 g of xylene were charged in a nitrogen atmosphere, and the mixture was heated to 120 DEG C and refluxed. A mixed solution prepared by mixing 143 g of the oligomer 1, 44 g of methacrylic acid, 58 g of methyl methacrylate, 141 g of ethyl acrylate, 15 g of tertiary amyl peroxyhexanoate as initiator and 105 g of xylene was uniformly added dropwise over 4 hours And then refluxed for 2 hours. The reaction mixture was then cooled to 60 ° C and subjected to an interim test (solid content: 51.8%, acid value: 150 mg KOH / g). 120 g of naphthenic acid, 44 g of zinc oxide, 62 g of xylene, and 5 g of ionized water were charged, and the temperature was raised to a reflux temperature of 100 캜. The mixture was refluxed at 100 ° C for 5 hours to obtain a solid resin content of 55.2%, a Gardner viscosity (25 ° C) Y to Z, and a brown transparent resin binder (B).

Synthesis Example 8: Binder (C) (Example 3)

A thermometer and a condenser, 116 g of butanol and 116 g of xylene were charged in a nitrogen atmosphere, and the mixture was heated to 120 DEG C and refluxed. A mixed solution obtained by mixing 212 g of the oligomer 2, 44 g of methacrylic acid, 42 g of methyl methacrylate, 87 g of ethyl acrylate, 15 g of tertiary amyl peroxyhexanoate as an initiator and 135 g of xylene was uniformly added over 4 hours The mixture was refluxed for 2 hours. The reaction mixture was then cooled to 60 ° C and subjected to an interim test (solid content: 51.8%, acid value: 150 mg KOH / g). 120 g of naphthenic acid, 44 g of zinc oxide, 62 g of xylene, and 5 g of ionized water were charged, and the temperature was raised to a reflux temperature of 100 캜. The mixture was refluxed at 100 ° C for 5 hours to obtain a solid resin component (C) having a solid content of 55.2%, a Gardner viscosity (25 ° C) Z and a brown color.

Synthesis Example 9: Binder (D) (Example 4)

A thermometer and a condenser, 116 g of butanol and 116 g of xylene were charged in a nitrogen atmosphere, and the mixture was heated to 120 DEG C and refluxed. A mixed solution prepared by mixing 198 g of oligomer 3, 44 g of methacrylic acid, 35 g of methyl methacrylate, 108 g of ethyl acrylate, 19 g of tertiary amyl peroxyhexanoate as initiator and 135 g of xylene was added dropwise uniformly for 4 hours And then refluxed for 2 hours. The reaction mixture was then cooled to 60 ° C and subjected to an interim test (solid content: 51.9%, acid value: 150 mg KOH / g). 119 g of naphthenic acid, 44 g of zinc oxide, 62 g of xylene, and 5 g of ionized water were charged and the temperature was raised to 100 DEG C at the reflux temperature. The mixture was refluxed at 100 ° C for 5 hours to obtain a solid resin component (D) having a solid content of 55.3%, a Gardner viscosity (25 ° C) Y and a brown color.

Synthesis Example 10: Binder (E) (Example 5)

A thermometer and a condenser, 130 g of butanol and 130 g of xylene were charged in a nitrogen atmosphere, and the mixture was heated to 120 DEG C and refluxed. A mixed solution prepared by mixing 263 g of oligomer 4, 70 g of methacrylic acid, 26 g of methyl methacrylate, 74 g of ethyl acrylate, 22 g of tertiary amyl peroxyhexanoate as initiator and 151 g of xylene was added dropwise uniformly for 4 hours And then refluxed for 2 hours. The reaction mixture was then cooled to 60 ° C and subjected to an interim test (solid content: 51.9%, acid value: 150 mg KOH / g). 80 g of naphthenic acid, 30 g of zinc oxide, 22 g of xylene, and 3 g of ionized water were charged and the temperature was raised to a reflux temperature of 100 캜. The mixture was refluxed at 100 DEG C for 8 hours to obtain a solid resin content of 55.2%, a Gardner viscosity (25 DEG C) Y to Z, and a brown transparent resin binder (E).

Synthesis Example 11: Binder (F) (Example 6)

A thermometer and a condenser, 124 g of butanol and 124 g of xylene were charged in a nitrogen atmosphere, and the mixture was heated to 120 ° C and refluxed. Then, 128 g of the oligomer 3, 51 g of methacrylic acid, 41 g of triisopropylsilyl acrylate, 29 g of methyl methacrylate, 165 g of ethyl acrylate, 50 g of tertiary amyl peroxyhexanoate as initiator and 145 g of xylene were mixed The mixed solution was homogeneously added dropwise over 4 hours and refluxed for 2 hours. The reaction mixture was then cooled to 60 ° C and subjected to an interim test (solid content: 52.6%, acid value: 125 mg KOH / g). 77 g of naphthenic acid, 28 g of zinc oxide, 33 g of xylene, and 3 g of ionized water were charged and the temperature was raised to a reflux temperature of 100 캜. And the mixture was refluxed at 100 DEG C for 8 hours to obtain a solid resin content of 55.1%, a Gardner viscosity (25 DEG C) Y, and a transparent resin binder (F)

Synthesis Example 12: Binder (G) (Comparative Example 1)

A thermometer and a condenser, 93 g of butanol and 93 g of xylene were charged in a nitrogen atmosphere, and the mixture was heated to 120 ° C and refluxed. Thereafter, a mixed solution prepared by mixing 71 g of methacrylic acid, 31 g of methyl methacrylate, 207 g of ethyl acrylate, 15 g of tertiary amyl peroxyhexanoate as initiator and 108 g of xylene was uniformly added dropwise over 4 hours, Lt; / RTI > Thereafter, the reaction mixture was cooled to 60 DEG C and subjected to an intermediate test (solid content: 51.9%, acid value: 150 mg KOH / g). 183 g of naphthenic acid, 67 g of zinc oxide, 124 g of xylene, and 7 g of ionized water were charged and the temperature was raised to a reflux temperature of 100 캜. The mixture was refluxed at 100 DEG C for 5 hours to obtain a solid content of 55.6%, a Gardner viscosity (25 DEG C), and a transparent resin binder (G) of brown color.

Synthesis Example 13: Binder (H) (Comparative Example 2)

A thermometer and a condenser, 96 g of butanol and 96 g of xylene were charged in a nitrogen atmosphere, and the mixture was heated to 120 DEG C and refluxed. Thereafter, 62 g of methacrylic acid, 48 g of methyl methacrylate, 163 g of ethyl acrylate, 32 g of triisopropylsilyl acrylate, 16 g of 2-methoxyethyl acrylate, 39 g of tertiary amyl peroxyhexanoate as an initiator, Was added dropwise uniformly over 4 hours, and the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was cooled to 60 ° C, subjected to an intermediate test (solid content: 51.4%, acid value: 125 mg KOH / g), 159 g of naphthenic acid, 58 g of zinc oxide, 90 g of xylene and 13 g of ionized water, Lt; / RTI > The mixture was refluxed at 100 占 폚 for 10 hours to obtain a solid content of 55.4%, a Gardner viscosity (25 占 폚) Z and a transparent resin binder (H) of brown color.

Preparation of antifouling paint composition: Examples 1 to 6 and Comparative Examples 1 to 2

The antifouling paint compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were respectively prepared according to the compositions of Table 1 using the binders prepared in Synthesis Examples 6 to 13, and their physical properties were evaluated and shown in Table 2.

Paint Property Evaluation

Paint solid

1) Test conditions: about 3.0 g of the prepared coating, sampling at 150 ° C for 24 hours

2) Solid (%): weight after heating / weight before heating × 100

Paint viscosity

Test conditions: Measurement at 25 ° C, Kreb's Unit

Press  exam

1) Specimen: 100 × 300 × 3 (mm) Steel plate

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

3) Antifouling paint: 300 ㎛ After painting 1 week Dry at room temperature (20 ℃)

4) Test conditions: 20 × 20 × 20 (mm) Stress after 50 kgf / ㎤ pressure for 40 minutes

5) Strain (%): 100- (film thickness after application of pressure / film thickness before applying pressure)

6) Evaluation Criteria

5: Less than 3%

4: 3% or more, less than 5%

3: 5% or more, less than 7%

2: 7% or more, less than 10%

1: 10% or more

Crack resistance  exam

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

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

3) Antifouling paint: 600 ㎛ After painting 1 week Dry at room temperature (20 ℃)

4) Test conditions: 23 ℃ sea water 24 hours immersion → 24 hours outdoor drying - 1 cycle

5) Evaluation Criteria

  ① Visual inspection of specimen crack after every cycle test

  ② Write cycle number when crack is found

Antifouling performance  exam

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

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

3) Antifouling paint: 300 ㎛ After painting 1 week Dry at room temperature (20 ℃)

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

5) Evaluation Criteria

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

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

3: A thick slime layer is observed, or the vegetation contaminated area is less than 20% of the effective area of the specimen

2: The condition that the vegetable contamination area exceeds 20% and 50% or less of the effective area of the specimen

1: The condition that the vegetable contamination area exceeds 50% and less than 100% of the effective area of the specimen

X: Animal contamination occurred

My discoloration property  Measure

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

2) Sample preparation: XL washing (dirt and debris removal) and drying

3) Antifouling paint: 250 ㎛ After painting 1 week Dry at room temperature (20 ℃)

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

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

Friction resistance measurement

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

2) Test condition: The specimen is left in seawater for 3 days, then it is rotated at 1,000 rpm, and the friction resistance is measured by torque meter (Torque: Ncm)

3) Evaluation method: Comparing the torque immediately after immersion and after 10-week immersion, with the torque of unstacked stainless steel as a standard

Immediately after leaving for 3 days after painting - Specimen Torque - Specimen before painting

After 10 weeks: After 10 weeks Torque - Painted paint Torque

Claims (9)

A resin for an antifouling paint obtained by reacting a copolymer in which a first monomer containing one double bond is reacted with a second monomer containing one carboxylic acid group and one double bond together with an organic acid and a divalent metal as,
Wherein the number of straight-chain elements connecting the double bond of the second monomer and the carboxylic acid group is 4 or more greater than the number of straight-chain elements connected to the double bond of the first monomer. delete The antifouling paint resin according to claim 1, wherein the first monomer and the second monomer are represented by formulas (1) and (2), respectively:
[Chemical Formula 1]

(2)

In Formula 1,
-X- is _{^{- (CR 1 R 2) a}} '-, - (CR 3 = CR 4) a''-, - (CO) a''' -, - (O) b -, - (NR 5) _c -, and - (S) _d - one selected from the group consisting of or or and least two linear combination of these, where R, R ^1, R ^2, R ^3, R ⁴ and R ⁵ are each independently hydrogen, , An aliphatic, alicyclic or aromatic hydrocarbon group,
a '', a ''', b, c, and d each represents an integer of 0 or more and represents the sum of the number of each connector contained in -X-,
1) + b + c + d + (the number of carbon atoms on the short side between the neighboring functional groups in the alicyclic hydrocarbon group and the respective carbon atoms in the alicyclic hydrocarbon group + 1) Lt;
In Formula 2,
-Y- is _{^{- (CR 6 R 7) e}} '-, - (CR 8 = CR 9) e''-, - (CO) e''' -, - (O) f -, - (NR 10) _g -, and - (S) _h - either one or or two or more linear combination of which are selected from the group consisting of, wherein Q, R ^6, R ^7, R ^8, R ⁹ and R ¹⁰ are each independently hydrogen, , An aliphatic, alicyclic or aromatic hydrocarbon group,
e ', e'', f, g, and h are integers of 0 or more and represent the sum of the number of each connector included in -Y-,
(the number of carbon atoms on the short side between the neighboring functional groups in the alicyclic hydrocarbon group and the carbon atoms in the alicyclic hydrocarbon group + 1 in the formula (2)) + m 'e' + (e "+ 1) + e ' to be. The resin for an antifouling paint according to claim 1, wherein the solid dispersion of the copolymer comprising the first monomer and the second monomer has a KOH / g of from 50 to 225 mg KOH / g. The organic acid according to claim 1, wherein the organic acid is selected from the group consisting of an aliphatic organic acid having 1 to 24 carbon atoms, an alicyclic organic acid having 3 to 24 carbon atoms, an aromatic organic acid having 6 to 24 carbon atoms, and a half ester resulting from the reaction of an acid anhydride with an alcohol One or more resins for antifouling paints. The resin for an antifouling paint according to claim 1, wherein the ^bivalent metal is at least one selected from the group consisting of Zn ²⁺ , Cu ²⁺ , Mn ²⁺ and Co ²⁺ . An antifouling paint composition comprising the resin for an antifouling paint according to any one of claims 1 to 6. 8. The composition according to claim 7, wherein, based on 100% by weight of the composition,
10 to 50% by weight of the resin for the antifouling paint;
10 to 60% by weight of antifouling;
0.1 to 20% by weight of an antifouling agent elution regulator; And
And 15 to 60% by weight of a solvent. Reacting a first monomer containing one polymerizable double bond with a second monomer containing one carboxylic acid group and one double bond to form a radical reaction product; And
Mixing the radical reaction product with a divalent metal and an organic acid,
Wherein the number of straight-chain elements connecting the double bond and the carboxyl group of the second monomer is 4 or more larger than the number of straight-chain elements connected to the polymerizable double bond of the first monomer.

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