KR101617725B1 - Resin for antifouling paint and antifouling paint composition comprising the same - Google Patents

Abstract

The present invention relates to a resin for an antifouling paint and an antifouling paint composition comprising the same, and more particularly to a resin for an antifouling paint and, more particularly, to an antifouling paint composition comprising a marine organism And to an antifouling paint composition containing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a resin for an antifouling paint and an antifouling paint composition containing the same. [0002]

The present invention relates to a resin for an antifouling paint and an antifouling paint composition comprising the same, and more particularly to a resin for an antifouling paint and, more particularly, to an antifouling paint composition comprising a marine organism And to an antifouling paint composition containing the same.

The coating composition to which the antifouling resin is applied is intended to prevent or control the attachment and growth of marine organisms causing surface contamination of the seawater-deposited coating film. When various marine organisms are attached to the surface of the film, the frictional force between the surface of the film and the sea water during the operation of the ship increases, which may increase the fuel cost, which is a large part of the operating expenses. The antifouling paint is a paint for preventing adhesion of such attachments and reducing the coefficient of friction between water and ship during operation.

Antifouling paints are water-insoluble types using water-insoluble binders and water-soluble types using water-soluble binders. The water-insoluble type is an antifouling paint prepared by adding a large amount of an antifouling agent such as copper nitrate and the like to an old-fashion antifouling paint using water-insoluble vinyl, a chlorinated rubber resin or the like. In the state that the water- The anti-fouling agent such as the ash acid in the inside gradually diffuses into seawater and exhibits the anti-fouling performance. The water-soluble type is a paint which is used together with an antifouling agent by mixing a water-insoluble resin and a resin soluble in water such as rosin. The antifouling agent contained in the coating film while the resin is dissolved in water exhibits the antifouling performance as seawater. The water-soluble type has a longer antifouling performance than the water-insoluble type, but the period of time in which the coating film does not melt uniformly and the antifouling performance is exhibited is within three years.

Currently widely used magnetic antimicrobial antifouling paint is a method in which water-insoluble resin is hydrolyzed by water-soluble resin and slowly dissolves into water-soluble resin, thereby releasing antifouling agent such as copper oxide. The rate of dissolution in seawater is uniformly controlled as compared with the previous water-soluble type, so that the long-term antifouling performance can be exhibited. Antifouling paints can be classified into tin type and non-refinement type depending on the presence or absence of tin compounds. Non-refinement type can be divided into metal type and silyl type again.

The tin type is a structure in which tributyl tin oxide is chemically bonded to the acrylic main chain. The alkali is hydrolyzed at a pH of 8 or higher to become a copolymer of acrylic acid, which gradually 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, negative factors such as malformation of fish and males in males became more prominent.

The non-ferrous metal type has a similar structure to the tin type. Acrylic acid or acid compound is a structure in which Zn or Cu is bonded to the acid compound, and it 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 high chemical stability and can be used for various antifouling agents, and has a more stable wear rate than the non-sapphire metal type. The silyl type acrylic monomers are high in cost, and the total raw material cost is high, which is a disadvantage. Since the abrasion rate at the time of anchoring is low, 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 can be used for a long period of time, functions to reduce fuel cost by reducing friction resistance with seawater, volatile organic compounds (VOC) And a function of reducing the content of the water.

International Patent Publication No. WO2009-007276 discloses a composition comprising A) a monomer comprising at least one ethylenically unsaturated bond and at least one silylester functionality, B) at least one monomer comprising two or more polymerizable ethylenically unsaturated bonds, C) An antifouling paint composition having excellent antifouling performance and workability can be produced by producing a resin having self-polishing characteristics using one or more chain transfer agents.

In International Patent Publication No. WO2009-031509, a metal salt bond-containing copolymer obtained by reacting (meth) acrylic acid with zinc or a copper compound was synthesized, followed by radical polymerization with other acrylic monomers to prepare a hydrolyzable resin. The resin thus prepared can be applied to an antifouling paint to produce a coating composition excellent in long-term antifouling property and having a uniform wear rate.

Korean Patent Laid-Open Publication No. 2013-0093840 discloses a process for producing an organic resin composition comprising the steps of: 1) dissolving an organic acid containing a carboxylic acid group and an amine group in a monomer mixture containing 2) a divalent metal and 3) a monomer containing a double bond and a carboxylic acid group, A resin for an antifouling paint prepared by a condensation reaction with an acrylic resin produced by a reaction and an antifouling paint composition containing the same are described. By applying an organic acid containing a carboxylic acid group and an amine group, physical properties such as discoloration resistance and crack resistance are improved.

Japanese Patent Application Laid-Open No. 2006-265560 discloses a coating film excellent in long-term antifouling performance and crack resistance by applying a monomer including a silyl group, a monomer including a metal ester, and a monomer containing an alkyl group.

There is a slight difference in the synthesis method of the above-mentioned magnetic antimicrobial antifouling resin depending on the non-refractory metal type and the silyl type. Typically, non-ferrous metal types can be divided into a first reaction and a second reaction. Acrylic acid-modified acrylic resin is prepared by copolymerizing an acrylic monomer including a (meth) acrylic acid monomer in a first reaction, and then reacted with a metal compound, a low molecular organic acid or the like in a second reaction to synthesize an ultimate antifouling resin. Since the silyl type type is an acrylic monomer having an alkylsilyl pendant group having a hydrolyzable group, it can be produced by a conventional radical polymerization method.

An object of the present invention is to provide a resin for an antifouling paint having physical properties improved in workability by applying a resin for a low viscosity or high solid content antifouling paint and an antifouling paint composition containing the same.

Disclosure of the Invention In order to accomplish the above object, the present invention provides a resin composition comprising: a first monomer comprising a carboxylic acid functional group and a polymerizable double bond-containing unsaturated hydrocarbon group; And a second monomer comprising a polymerizable double bond-containing unsaturated hydrocarbon group, wherein the number of linear elements connected to the polymerizable double bond of the second monomer is greater than the number of the polymerization of the first monomer Wherein the number of the double bonds and the number of straight chain elements connecting the carboxylic acid functional groups is 5 or more.

That is, the number of the linear chain elements connected to the polymerizable double bond is a monomer containing a polymerizable double bond-containing unsaturated hydrocarbon group, and the number of the linear chain elements connected to the polymerizable double bond Monomers having a number smaller than the number of the elements or 1 to 4 or more are not included in the resin for the antifouling paint of the present invention as the second monomer.

In one embodiment of the present invention, the content of the second monomer may be determined based on the solid content of the radical reaction product, the content of the first monomer in the solid component of the radical reaction product excluding the monomer capable of hydrolysis Of not less than 80% by weight.

In yet another embodiment,

The first monomer is represented by the following general formula (1)

[Chemical Formula 1]

Wherein -X- is a single bond, C ₃ or more, preferably C ₃ to C ₆₀ divalent cycloaliphatic, C ₁ or more, preferably C ₁ to C ₆₀ divalent heteroaliphatic rings, C ₆ or more, C ₆ ~ C ₆₀ (includes this N, O, S, and at least one heteroatom selected atom from P) aromatic, C ₃ or more preferably a C ₃ ~ C ₆₀ ^{heteroaromatic, - (CR 1 R 2)} a '- ^{, - (CR 3 = CR 4} ) a '' -, - (CO) a '''-, - (O) b -, - (NR 5) c -, - (CR 6 = C = CR 7) a _'''' -, and - (S) _d -, and any one or a or a linear combination of two or more of those selected from the group consisting of wherein ^{R, R 1, R 2,} R 3, R 4, R 5, R 6 And R ⁷ each independently represents a hydrogen atom or an organic group (for example, an aliphatic, alicyclic, and aromatic hydrocarbon group), and a ', a ", a'", a " d is an integer of 0 or more and n = a '+ (a''+ 1) + a''' + a '''+ 2 + b + c + d + The carbon that binds each of the functional groups + 2), wherein when n = 0, X is a single bond,

The second monomer is represented by the following formula (2)

(2)

Here, -Y- is C ₃ or more preferably a C ₃ ~ C 2 is alicyclic, or more C _{1 to 60} and preferably C ₁ ~ C ₆₀ heteroaryl 2 is an aliphatic ring of, C ₆ or higher and preferably C ₆ ~ C ₆ aromatics, C ₃ or higher, preferably C ₃ to C ₆₀ heteroaromatic (wherein at least one hetero atom selected from N, O, S and P is included), - (CR ⁸ R ⁹ ) _{e ' ^{CR 10 = CR 11) e '}} ' -, - (CO) e '''-, - (O) f -, - (NR 12) g -, - (CR 13 = C = CR 14) e'''_'- and - (S) _h -, and any one or a or a linear combination of two or more of those selected from the group consisting of where ^{Q, R 8, R 9,} R 10, R 11, R 12, R 13 and R ¹⁴ E ', e'',e''', f, g, and h represent independently a hydrogen atom or an organic group (e.g., an aliphatic, alicyclic, and aromatic hydrocarbon group) (2) + f + g + h + (wherein m = e '+ e''+ 1) + e' Bonding carbon + 2 carbon atoms of the smaller side) is characterized in that ≥ n + 5.

In another aspect, the present invention provides an antifouling paint composition comprising the resin for an antifouling paint.

On the other hand, in another aspect, the present invention provides a process for preparing a polymer comprising: a) a first monomer comprising a carboxylic acid functional group and a polymerizable double bond-containing unsaturated hydrocarbon group; And a second monomer comprising a polymerizable double bond-containing unsaturated hydrocarbon, to form a radical reaction product; And b) reacting the radical reaction product with a divalent metal and a low molecular organic acid, wherein the number of linear elements connected to the polymerizable double bond of the second monomer is such that the polymerization of the first monomer Wherein the number of the double bonds is 5 or more than the number of elements in the linear chain connecting the functional double bond and the carboxylic acid functional group.

The resin for an antifouling paint according to the present invention improves workability with a low viscosity or a high solids content and has excellent physical properties. Therefore, the topcoat of a paint applied to a hull outside and an underwater structure of a ship ), Which can be suitably used for an antifouling paint applied to prevent adhesion and growth of marine life.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic view showing a barrier effect of a second monomer in a resin for an antifouling paint of the present invention. FIG.

Hereinafter, the present invention will be described in detail.

The production of the resin for an antifouling paint of the present invention can be carried out by a first reaction and a second reaction. The first reaction is a conventional radical reaction, and the second reaction is a condensation reaction of the result of the first reaction with a bivalent metal and a low molecular organic acid containing a carboxylic acid.

In the first radical reaction, a first monomer containing a carboxylic acid functional group and a double bond (unsaturated hydrocarbon) serving as a hydrolysis; Wherein the number of the linear chain elements connected to the polymerizable double bond of the second monomer is larger than the number of the polymerizable double bonds of the first monomer, More than 5 times the number of the double bond and the number of the elements in the straight chain connecting the carboxylic acid functional group) to produce a first reaction product. The first monomer and the second monomer may be represented by the following formulas (1) and (2), respectively.

[Chemical Formula 1]

In Formula 1, -X- represents a single bond, a C ₃ or more, preferably a C ₃ to C ₆₀ bivalent alicyclic group, a C ₁ or more, preferably a C ₁ to C ₆₀ divalent heteroaliphatic ring, a C ₆ or more Preferably at least one C ₆ to C ₆₀ aromatic, C ₃ or more, preferably C ₃ to C ₆₀ heteroaromatic (wherein at least one hetero atom selected from N, O, S and P is included), - (CR ¹ R ² ) ^{_{a '-, - (CR 3}} = CR 4) a''-, - (CO) a''' -, - (O) b -, - (NR 5) c -, - (CR 6 = C = CR ⁷⁾ _{a ''''} -, and - (S) _d -, and any one or a or a linear combination of two or more of those selected from the group consisting of wherein R, R ^1, R ^2, R ^3, R ^4, R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an organic group (for example, an aliphatic, alicyclic or aromatic hydrocarbon group)

a '', a '' ', a' '' ', b, c, and d are integers of 0 or more,

(2) + b + c + d + (between the carbon of the bivalent aliphatic ring which is bonded to the adjacent functional group, respectively) The number of carbon atoms on the short side + 2), wherein when n = 0, X is a single bond.

(2)

Here, -Y- is C ₃ or more preferably a C ₃ ~ C 2 is alicyclic, or more C _{1 to 60} and preferably C ₁ ~ C ₆₀ heteroaryl 2 is an aliphatic ring of, C ₆ or higher and preferably C ₆ ~ C ₆ aromatics, C ₃ or higher, preferably C ₃ to C ₆₀ heteroaromatic (wherein at least one hetero atom selected from N, O, S and P is included), - (CR ⁸ R ⁹ ) _{e ' ^{CR 10 = CR 11) e '}} ' -, - (CO) e '''-, - (O) f -, - (NR 12) g -, - (CR 13 = C = CR 14) e'''_'- and - (S) _h -, and any one or two or more of these, or a linear combination are selected from the group consisting of,

Wherein ^{Q, R 8, R 9,} R 10, R 11, R 12, R 13 and R ¹⁴ each independently represent a hydrogen atom or an organic group (for example, aliphatic, cycloaliphatic and aromatic hydrocarbon groups),

e ', e' ', e' '', f ', g and h are integers of 1 or more,

(2) + f + g + h + (between the carbon of the bivalent aliphatic ring which is bonded with the neighboring functional group, respectively) + 2) > = n + 5).

The radical reaction product (first reaction product) prepared from the first and second monomers is reacted with a divalent metal and a low molecular weight organic acid to produce a secondary product.

When the resin prepared according to the present invention is applied to paints, the interaction between metal esters or between metal esters and silyl groups can be prevented by a barrier effect as shown in Fig. 1, A resin for a solid part antifouling paint and a coating composition containing the same can be provided.

The solvent which can be used in the first reaction is not particularly limited so long as it does not adversely affect the reaction, but aromatic solvents such as toluene and xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, ethyl propyl ketone, methyl Ketone type solvents such as isobutyl ketone and methylaryl ketone, ketone solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, isopropyl acetate, butyl acetate, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate , Ester solvents such as carbitol acetate, and alcohol solvents such as n-propanol, isopropanol, n-butanol, isobutanol, and 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 first reaction product

The result of the first reaction is a monomer (first monomer) comprising a double bond and a carboxylic acid group; And a monomer containing a double bond and an alkyl group (second monomer). The monomer containing a double bond and a carboxylic acid group is not limited in its structure if it contains an unsaturated hydrocarbon and a carboxylic acid group.

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

In another embodiment, the first monomer may be acrylic acid represented by the following formula (3): wherein R = H, n = 0.

(3)

In another embodiment, the first monomer may be an oligomer prepared by the ring-opening reaction of 2-hydroxyethyl acrylate and maleic anhydride, represented by the following formula (4) in this case X is the order of _{- (CO) a '''} -, - (O) b -, - (CR 1 R 2) a' -, - (O) b -, - (CO) a ''' -, and - (CR ³ ═CR ⁴ ) _{a "} -, wherein R═CH ₃ , R ¹ = R ² = R ³ = R ⁴ = H, where a '''= 1, b = 1, a' = 2, a '' = 1 and thus n = 8.

[Chemical Formula 4]

In another embodiment, the first monomer may be an oligomer prepared by the ring opening reaction of [W] 8-hydroxyethyl acrylate with hexahydrophthalic anhydride , represented by the following formula (5) in this case X is the order of _{- (CO) a '''} -, - (O) b -, - (CR 1 R 2) a' -, - (O) b -, - (CO) a ''' - and a linear aliphatic ring of C < ₆ > wherein R = H, R < ^{1 &} = R ² = H, wherein a '''= 1, b = 1, a' = 2, and "the carbon number of the side of the bivalent aliphatic ring and the carbon to which each neighboring functional group is bonded + 2" = 2 . Therefore, n = 8.

[Chemical Formula 5]

In one embodiment, the monomer (second monomer) comprising the double bond and the alkyl group may be represented by the formula (2).

The content of the second monomer including a double bond and an alkyl group is determined based on the solids content of the radical reaction product by hydrolysis including a first monomer containing a double bond and a carboxylic acid functional group in the solid content of the radical reaction product (Based on solid content) of the content excluding the monomer that can be used. If the content of the second monomer is less than 80% by weight (based on the solids content) of the monomer excluding the monomer capable of hydrolyzing, such as the first monomer containing a double bond and a carboxylic acid functional group, the viscosity may not be lowered. The monomer capable of hydrolysis is preferably a monomer containing a silyl group, more preferably a monomer comprising a silyl group, and more preferably a monomer comprising trimethylsilyl acrylate, triisopropylsilyl acrylate, triisopropylsilyl methacrylate, tributylsilyl methacrylate or the like Lt; / RTI >

In one aspect of the present invention, when the second monomer contains a carboxylic acid group, it may be a first monomer. For example, methacrylic acid is n = 0 for the first monomer, but m = 2 for the second monomer. Preferably, the second monomer may not contain a carboxylic acid group.

The primary reaction product by the radical reaction of the present invention can be produced by a conventional radical polymerization method. The radical reaction product preferably has a solid content of 10 to 90% by weight based on the total weight of the radical reaction product and a solid acid value of 50 to 225 mgKOH / g based on the solid content. If the solid content is less than 10%, the abrasion resistance and discoloration resistance may be deteriorated. If the solid content is more than 90%, the reaction temperature control may not be performed. If the acid value is less than 50 mgKOH / g, the abrasion rate, the antifouling property and the discoloration resistance may be lowered. If the acid value is more than 225 mgKOH / g, the crack resistance may be lowered and the abrasion rate may be higher than necessary .

Bivalent metal

The divalent metal used in the synthesis of the resin for an antifouling paint of the present invention plays a role of generating a bond that enables the coating film to be abraded by hydrolysis in seawater and preferably Zn ^{2 +} , Cu ^{2 +} , Mn ²⁺ and Co ^{2 +,} and the like, but the present invention is not limited thereto.

Carboxylic acid  Included Low molecular weight  Organic acid

The low molecular weight organic acid including a carboxylic acid 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. A low molecular weight organic acids, as containing one functional, bifunctional or polyhydric least three functional groups, the aromatic acid of the C ₁ ~ C ₂₄ aliphatic acids, C ₃ ~ C ₂₄ aliphatic acid and a C ₆ ~ C ₂₄ of the At least one selected from the group consisting of 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, a half ester generated from the reaction of an acid anhydride with an alcohol with a low molecular weight organic acid containing a carboxylic acid may be used instead. As the acid anhydride, at least _one selected from the group consisting of C ₁ to C ₂₄ aliphatic, C ₃ to C ₂₄ alicyclic, and C ₆ to C ₂₄ aromatic acid anhydrides can be used, and the acid anhydride monomer C ₁ ~ C and ₂₄ aliphatic, C ₃ ~ aromatic anhydride of C ₂₄ cycloaliphatic or C ₆ ~ C ₂₄ of the, preferably succinic anhydride, maleic anhydride, dodecyl succinic anhydride, dioctyl succinic anhydride, phthalic anhydride, hexahydrophthalic (PMDA), 3,3 ', 4,4-oxydiphthalic acid dianhydride (ODPA), 3, 3, 4, 4-dioxane dihydrophthalic acid anhydride, hydroxycarboxylic acid anhydride, hydroxycarboxylic acid anhydride, hydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, pyromellitic acid dianhydride (6FDA), benzoquinonetetracarboxylic acid dianhydride, 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-diphthalic acid (hexafluoroisopropylidene) anhydride Tetracarboxylic acid dianhydride and (meth) acrylic acid anhydride. Lure which is at least one selected from the group. Examples of the alcohol include monohydric 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.

Antifouling paint  Composition

The antifouling paint composition of the present invention uses the resin for an antifouling paint of the present invention as a binder component, and the antifouling component contained in the coating film while the resin is hydrolyzed in water exerts its antifouling performance through seawater. 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, the antifouling agent may further comprise an antifouling agent elution controlling agent capable of controlling the long-term antifouling performance by controlling the antifouling agent and the antifouling agent elution.

The antifouling agent elution controlling agent of the present invention controls the antifouling agent elution rate 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.

The antifouling agent elution controlling agent is preferably contained in an amount of 0.1 to 25% by weight (in terms of solid content) based on the total weight of the antifouling paint composition, and such a compounding ratio can be determined from the viewpoint of antifouling performance and water resistance of the coating film.

A known antifouling agent in the form of organic or inorganic compound as an additive, a pigment component such as zinc oxide which acts to improve the film strength, control the wear rate and coloring, anti-sagging agent, anti-settling agent, Plasticizers such as paraffin chloride, acrylic resins, and polyalkyl vinyl ethers (vinyl ether (co) polymers), which contribute to improving the crack resistance of the film, and defoaming agents. 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.

According to the present invention, it is possible to provide a resin for an antifouling paint having an improved workability by applying a resin having a low viscosity or a high solids content for an antifouling paint, and an antifouling paint composition containing the same.

The present invention will be described in more detail by way of the following examples. However, the present invention is not limited to those described in the following examples.

[ Example ]

For antifouling paints  Manufacture of resin

Comparative Example  One

A thermometer and a condenser, 300 g of butanol and 300 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 230 g of methacrylic acid, 385 g of ethyl acrylate, 385 g of butyl acrylate, 120 g of tertiary amyl peroxyhexanoate as an initiator and 350 g of xylene was added dropwise uniformly over 4 hours and refluxed for 2 hours The mixture was cooled to 60 DEG C and 591 g of naphthenic acid, 218 g of zinc oxide, 450 g of xylene and 24 g of ionized water were charged and the temperature was raised to 100 DEG C at a reflux temperature. The reflux was maintained at 100 DEG C for 5 hours to obtain a transparent resin having a solid content of 55.2%, a Gardner viscosity (25 DEG C) Z, and a brown color.

Comparative Example  2

A thermometer and a condenser, 300 g of butanol and 300 g of xylene were charged in a nitrogen atmosphere, and the mixture was heated to 120 DEG C and refluxed. Then, 230 g of methacrylic acid and 770 g of ethyl acrylate, 120 g of tertiary amyl peroxyhexanoate as an initiator, and 350 g of xylene were separately added dropwise uniformly over 4 hours, reflux was maintained for 2 hours, After cooling to 60 캜, 591 g of naphthenic acid, 218 g of zinc oxide, 450 g of xylene and 24 g of ionized water were charged and the temperature was raised to 100 캜 at the reflux temperature. The reflux was maintained at 100 DEG C for 5 hours to obtain a transparent resin having a solid content of 55.3%, a Gardner viscosity (25 DEG C) Z2, and a brown color.

Comparative Example  3

A thermometer and a condenser, 300 g of butanol and 300 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 175 g of methacrylic acid, 340 g of ethyl acrylate, 335 g of butyl acrylate, 150 g of triisopropylsilyl acrylate, 150 g of tertiary amyl peroxyhexanoate as an initiator and 350 g of xylene was stirred for 4 hours After refluxing was maintained for 2 hours, the mixture was cooled to 60 ° C, and 446 g of naphthenic acid, 164 g of zinc oxide, 300 g of xylene and 36 g of ionized water were charged and the temperature was raised to 100 ° C. at the reflux temperature. The reflux was maintained at 100 ° C for 5 hours to obtain a transparent resin having a solid content of 55.3%, a Gardner viscosity (25 ° C) Y, and a brown color.

Comparative Example  4

A thermometer and a condenser, 300 g of butanol and 300 g of xylene were charged in a nitrogen atmosphere, and the mixture was heated to 120 DEG C and refluxed. Then, 305 g of 2-carboxylethyl acrylate, 695 g of butyl acrylate, 50 g of tertiary amyl peroxyhexanoate as an initiator, and 350 g of xylene were separately added, and the mixture was homogeneously added dropwise over 4 hours and refluxed for 2 hours After cooling, the mixture was cooled to 60 deg. C and 591 g of naphthenic acid, 218 g of zinc oxide, 420 g of xylene and 24 g of ionized water were charged and the temperature was raised to a reflux temperature of 100 deg. The reflux was maintained at 100 DEG C for 5 hours to obtain a transparent resin having a solid content of 55.3%, a Gardner viscosity (25 DEG C) Z, and a brown color.

Oligomer  1

A thermometer and a condenser was charged with 784 g of 2-hydroxyethyl acrylate, 0.4 g of butylated hydroxytoluene and 1,012 g of hexahydrophthalic anhydride in a nitrogen atmosphere, and the mixture was heated to 90 DEG C and maintained for 6 hours . An acid value of 205 mg KOH / g, a Gardner viscosity (25 캜) U, and a light brown transparent oligomer.

Comparative Example  5

A thermometer and a condenser, 300 g of butanol and 300 g of xylene were charged in a nitrogen atmosphere, and the mixture was heated to 120 DEG C and refluxed. Then, a mixed solution prepared by mixing 256 g of the oligomer 1, 150 g of methacrylic acid, 594 g of butyl acrylate, 80 g of tertiary amyl peroxyhexanoate as initiator and 350 g of xylene was added dropwise uniformly over 4 hours, After refluxing was maintained, the mixture was cooled to 60 deg. C and 591 g of naphthenic acid, 218 g of zinc oxide, 400 g of xylene and 48 g of ionized water were charged and the temperature was raised to a reflux temperature of 100 deg. The reflux was maintained at 100 占 폚 for 8 hours to obtain a solid resin of 55.4%, a Gardner viscosity (25 占 폚) Z2, and a brown transparent resin.

Example  One

A thermometer and a condenser, 300 g of butanol and 300 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 230 g of methacrylic acid, 770 g of butyl acrylate, 120 g of tertiary amyl peroxyhexanoate as an initiator and 350 g of xylene was uniformly added dropwise over 4 hours, reflux was maintained for 2 hours, After cooling to 60 캜, 591 g of naphthenic acid, 218 g of zinc oxide, 450 g of xylene and 24 g of ionized water were charged and the temperature was raised to 100 캜 at the reflux temperature. The reflux was maintained at 100 DEG C for 5 hours to obtain a transparent resin having a solid content of 55.2%, a Gardner viscosity (25 DEG C) K, and a brown color.

Example  2

A thermometer and a condenser, 300 g of butanol and 300 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 175 g of methacrylic acid, 675 g of butyl acrylate, 150 g of triisopropylsilyl acrylate, 150 g of tertiary amyl peroxyhexanoate as an initiator and 350 g of xylene was added dropwise uniformly over 4 hours, and 2 The mixture was cooled to 60 ° C, and 446 g of naphthenic acid, 164 g of zinc oxide, 300 g of xylene and 36 g of ionized water were added thereto, and the temperature was raised to 100 ° C. at the reflux temperature. The reflux was maintained at 100 DEG C for 5 hours to obtain a transparent resin having a solid content of 55.3%, a Gardner viscosity (25 DEG C) I, and a brown color.

Example  3

A thermometer and a condenser, 300 g of butanol and 300 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 305 g of 2-carboxylethyl acrylate and 695 g of octyl methacrylate, 50 g of tertiary amyl peroxyhexanoate as an initiator and 350 g of xylene was added dropwise uniformly over 4 hours and refluxed for 2 hours And the mixture was cooled to 60 deg. C, 591 g of naphthenic acid, 218 g of zinc oxide, 420 g of xylene and 24 g of ionized water were charged and the temperature was raised to 100 DEG C at the reflux temperature. The reflux was maintained at 100 DEG C for 5 hours to obtain a transparent resin having a solid content of 55.3%, a Gardner viscosity (25 DEG C) Z, and a brown color.

Example  4

A thermometer and a condenser, 300 g of butanol and 300 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 256 g of the oligomer 1 prepared above, 150 g of methacrylic acid, 594 g of lauryl methacrylate, 80 g of tertiary amyl peroxyhexanoate as an initiator and 350 g of xylene was uniformly added dropwise over 4 hours After refluxing was maintained for 2 hours, the mixture was cooled to 60 ° C and 591 g of naphthenic acid, 218 g of zinc oxide, 400 g of xylene and 48 g of ionized water were charged and the temperature was raised to 100 ° C. at the reflux temperature. The reflux was maintained at 100 DEG C for 8 hours to obtain a solid resin of 55.4%, a Gardner viscosity (25 DEG C) P, and a transparent resin of brown color.

[Description of raw materials used]

1. Xylene: Mixed Xylene [SK Chemical]

2. Butanol: n-Butyl alcohol [Hanwha Chemical Co., Ltd.]

3. Methacrylic acid: Methacrylic acid [LG MMA]

4. Ethyl Acrylate: Ethyl Acrylate [LG Chem]

5. Butyl acrylate: n-Butyl acrylate [LG Chem]

6. Tertiary amyl peroxyhexanoate: Luperox 575 (Century Akeema Co., Ltd.)

7. Triisopropylsilyl acrylate: TIPX [YUKI GOSEI KOGYO., LTD.]

8. 2-Carboxyl ethyl acrylate: 2-Carboxyethyl acrylate [Sigma-Aldrich]

9. 2-Ethylhexyl acrylate: 2-Hexylethyl acrylate [Nippon Shokubai]

10. Butylated hydroxytoluene: IONOL CP [DEGUSSA SANT CELONI S.A.]

11. Hexahydrophthalic anhydride: HHPA [Dixie chemical company Inc.]

12. Octyl methacrylate: Octyl acrylate [Sigma-Aldrich]]

13. Lauryl methacrylate: MIRAMER M121 [MIWON]

14. Naphthenic acid: Naphthenic acid [MERICHEM COMPANY]

15. Zinc oxide: zinc oxide [Hanil Chemical Industry Co., Ltd.]

Antifouling paint  Preparation of composition

Comparative Example  6 to 10 and Example  5 ~ 8

An antifouling paint composition comprising the resins of Comparative Examples 1 to 5 and Examples 1 to 4 as the binder component was prepared with the composition shown in Table 1 and the physical properties were evaluated.

week)

16. Rosin: gum Rosin [Jianxi sino native products]

17. Plasticizer: Paraffin plastoil 152 [Handy chemical corporation]

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

19. Titanium back: TIPAQUE CR-97 [Ishihara Sangyo Kaisha, Ltd.]

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

21. Copper salt pyrithione: Copper Omadine Powder [Arch UK biocide Ltd]

22. Aliphatic amide wax paste: Monoral 5500M [HS Chem.]

23. Copper oxide: Red Copp 97N Premium [American Chemet]

The physical properties of the antifouling paint composition are evaluated as follows.

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

3: strain 5 to 7%, 2: strain 7 to 10%, 1: strain 10% or more) [5: strain less than 3%

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 - 30 times repeated

5) Evaluation Criteria

5: No cracks or visible defects; 4: Less than 5% of the total area of the specimen cracks; 3: 5 to 20% of the total area of the specimen cracks; 2: ~ 50% cracks occurred, 1: 50 ~ 70% cracks occurred in the total area of test specimen, 0: 70%

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

3: a state in which a thick slime layer is observed or the area of vegetable contamination is less than 20% of the effective area of the specimen; 2: a state in which no slip layer is observed; 1) the vegetable contaminated area is 50 to 100% of the effective area of the specimen; and X: the contaminated animal is in the state of contamination;

My discoloration property  Measure

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

2) Sample preparation: XL washing 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)

Claims (10)

A first monomer comprising an unsaturated hydrocarbon group containing a carboxylic acid functional group and a polymerizable double bond; And
A second monomer comprising an unsaturated hydrocarbon group comprising a polymerizable double bond;
Wherein the number of linear elements connected to the polymerizable double bond of the second monomer is 5 or more larger than the number of linear elements connecting the polymerizable double bond of the first monomer and the carboxylic acid functional group,
Wherein the content of the second monomer in the radical reaction product is 80 wt% or less based on the solid content of the radical reaction product excluding the monomer capable of hydrolyzing including the first monomer in the solid component of the radical reaction product % Or more,
Resin for antifouling paints. delete The antifouling paint according to claim 1, wherein the first monomer is represented by the following formula (1), and the second monomer is represented by the following formula (2)
[Chemical Formula 1]

Here, -X- is a single bond, C ₃ ~ C ₆₀ 2 The alicyclic ring, C ₁ ~ C ₆₀ 2 of the hetero-alicyclic, C ₆ ~ C ₆₀ 2 the aromatic ring, N, O in, and the S - (CR ¹ R ² ) _{a '} -, - (CR ³ ═CR ⁴ ) _a'' -, - (CO) ² -, or _a divalent heteroaromatic ring of C ₃ to C ₆₀ containing at least one heteroatom selected from _{a '''-, - (} O) b -, - (NR 5) c -, - (CR 6 = c = CR 7) a' is selected from the group consisting of - _'''-, and - (S) _d R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an organic group, and a ', a a '', a ''', b, c, and d are integers greater than or equal to zero and n = a' + + 2) + b + c + d + (the number of carbon atoms on the short side between the adjacent functional groups of the bivalent alicyclic, heteroaliphatic, aromatic or heteroaromatic ring and the respective carbon + 2) Wherein X is a single bond,
(2)

Here, -Y- is C ₃ ~ C ₆₀ 2 of the cycloaliphatic ring, C ₁ ~ C ₆₀ of the second hetero-alicyclic, C ₆ ~ C ₆₀ of the second ring, N, O, S and P is selected from - (CR ⁸ R ⁹ ) _{e '} -, - (CR ¹⁰ ═CR ¹¹ ) _{e "} -, - (CO) _e'' , wherein R is a divalent heteroaromatic ring of C ₃ to C ₆₀ containing at least one heteroatom, _{'-, - (O) f} -, - (NR 12) g -, - (CR 13 = C = CR 14) e''''- , and - (S) _h - or any one selected from the group consisting of Or a linear bond of two or more of them, wherein Q, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an organic group, e ''',e'''', f, g, and h are integers of one or more, m = e' + + f + g + h + (the number of carbon atoms on the short side between the adjacent functional groups of the bivalent alicyclic, heteroaliphatic, aromatic or heteroaromatic ring and the respective carbon + 2)? n + 5. 2. The antifouling paint according to claim 1, wherein the radical reaction product has a solid content of 10 to 90% by weight based on the total weight of the radical reaction product and an acid value of solid content of 50 to 225 mgKOH / g based on the solid content Suzy. A radical reaction product of a first monomer and a second monomer; A divalent metal; And a low molecular weight organic acid,
Wherein the first monomer comprises an unsaturated hydrocarbon group comprising a carboxylic acid functional group and a polymerizable double bond,
Wherein the second monomer comprises an unsaturated hydrocarbon group comprising a polymerizable double bond,
Wherein the number of linear elements connected to the polymerizable double bond of the second monomer is 5 or more larger than the number of linear elements connecting the polymerizable double bond of the first monomer and the carboxylic acid functional group,
Wherein the content of the second monomer in the radical reaction product is 80 wt% or less based on the solid content of the radical reaction product excluding the monomer capable of hydrolyzing including the first monomer in the solid component of the radical reaction product % Or more,
Resin for antifouling paints. An antifouling paint composition comprising the resin for an antifouling paint according to any one of claims 1 to 5. 7. The antifouling paint composition according to claim 6, further comprising: And an antifouling agent elution controlling agent selected from the group consisting of rosins, rosin derivatives, monocarboxylic acids and salts thereof. The antifouling paint composition according to claim 6, further comprising a pigment, an anti-flow agent, an anti-settling agent, a plasticizer, a defoaming agent and a solvent. a) a first monomer comprising an unsaturated hydrocarbon group containing a carboxylic acid functional group and a polymerizable double bond; And a second monomer comprising an unsaturated hydrocarbon group containing a polymerizable double bond, to form a radical reaction product; And
b) reacting the radical reaction product with a divalent metal and a low molecular weight organic acid,
Wherein the number of linear elements connected to the polymerizable double bond of the second monomer is at least 5 or more than the number of linear elements connecting the polymerizable double bond of the first monomer and the carboxylic acid functional group,
Wherein the content of the second monomer in the radical reaction product is 80 wt% or less based on the solid content of the radical reaction product excluding the monomer capable of hydrolyzing including the first monomer in the solid component of the radical reaction product % Or more,
A method for producing a resin for an antifouling paint. The method of producing a resin for an antifouling paint according to claim 9, wherein the first monomer is represented by the following formula (1), and the second monomer is represented by the following formula (2)
[Chemical Formula 1]

Here, -X- is a single bond, C ₃ ~ C ₆₀ 2 The alicyclic ring, C ₁ ~ C ₆₀ 2 of the hetero-alicyclic, C ₆ ~ C ₆₀ 2 the aromatic ring, N, O in, and the S - (CR ¹ R ² ) _{a '} -, - (CR ³ ═CR ⁴ ) _a'' -, - (CO) ² -, or _a divalent heteroaromatic ring of C ₃ to C ₆₀ containing at least one heteroatom selected from _{a '''-, - (} O) b -, - (NR 5) c -, - (CR 6 = C = CR 7) a' is selected from the group consisting of - _'''-, and - (S) _d R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an organic group, and a ', a a '', a ''', b, c, and d are integers greater than or equal to zero and n = a' + + 2) + b + c + d + (the number of carbon atoms on the short side between the adjacent functional groups of the bivalent alicyclic, heteroaliphatic, aromatic or heteroaromatic ring and the respective carbon + 2) Wherein X is a single bond,
(2)

Here, -Y- is C ₃ ~ C ₆₀ 2 of the cycloaliphatic ring, C ₁ ~ C ₆₀ of the second hetero-alicyclic, C ₆ ~ C ₆₀ of the second ring, N, O, S and P is selected from - (CR ⁸ R ⁹ ) _{e '} -, - (CR ¹⁰ ═CR ¹¹ ) _{e "} -, - (CO) _e'' , wherein R is a divalent heteroaromatic ring of C ₃ to C ₆₀ containing at least one heteroatom, _{'-, - (O) f} -, - (NR 12) g -, - (CR 13 = C = CR 14) e''''- , and - (S) _h - or any one selected from the group consisting of Or a linear bond of two or more of them, wherein Q, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an organic group, e ''',e'''', f, g, and h are integers of one or more, m = e' + + f + g + h + (the number of carbon atoms on the short side between the adjacent functional groups of the bivalent alicyclic, heteroaliphatic, aromatic or heteroaromatic ring and the respective carbon + 2)? n + 5.

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