KR101879458B1 - Resin for antifouling patint having excellent discoloration-resistance and crack-resistance and antifouling paint composition comprising the same - Google Patents

Abstract

The present invention relates to a resin for use in an antifouling paint applied to prevent adhesion and growth of marine life as a top coat of a coating film applied to a hull outside and an underwater structure of a ship, Specifically, the present invention relates to an antifouling paint composition, which comprises A) an acrylic resin prepared by radical reaction of a monomer containing a double bond and a carboxylic acid group and a monomer containing a double bond and an alkyl group, or a monomer and an acid group containing an alcohol group A polyester resin prepared by a condensation reaction of monomers included; B) a divalent metal; And C) an organic acid comprising a carboxylic acid group and an amine group, and an antifouling paint composition containing the same. According to the present invention, discoloration resistance and crack resistance can be improved.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin for an antifouling paint improved in discoloration resistance and crack resistance and an antifouling paint composition containing the same.

The present invention relates to a resin for use in an antifouling paint applied to prevent adhesion and growth of marine life as a top coat of a coating film applied to a hull outside and an underwater structure of a ship, To an antifouling paint composition.

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 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 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 suboxide-dissimilar antifouling agent gradually diffuses into seawater to exhibit the antifouling performance. The water-soluble type is a paint used together with an antifouling agent by mixing an insoluble resin and a molten resin 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 insoluble type, but the time period during which the coating film does not melt uniformly and the antifouling performance is exhibited is within three years.

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 an acrylic main chain. The alkali is hydrolyzed at an alkali of pH 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 fish malformation and female males became more important.

The non-ferrous metal type has a similar structure to the tin type. It is made of acrylic acid or acid compound with Zn or Cu bonded to it. 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.

The silyl type has high chemical stability and can use various antifouling agents and has a more stable wear rate than non-metal type 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.

U.S. Patent No. 3,167,473 and British Patent No. 1,475,590 disclose that a copolymer composed of a monomer in which a tributyl tin is bonded to an unsaturated carboxylic acid in salt form and a known acrylic unsaturated monomer, An antifouling paint composition prepared by mixing pigment components is disclosed. The copolymer exhibited good antifouling performance and uniform wear performance, but was subject to regulation due to biological problems of tin-based compounds eluted during hydrolysis. In 2003, a tin-based antifouling paint use inhibition treaty was concluded.

Japanese Patent No. 78-21889 discloses a method in which a metal ester compound such as zinc acetate is mixed with a copolymer having a carboxyl group in the side chain to partially gel a binder to an antifouling paint composition. The antifouling paint composition containing the copolymer has a problem that it is difficult to apply because of the poor coating film forming ability and paint retention property and cracks or peel phenomenon due to wear and high viscosity.

Japanese Patent No. 81-165992 and No. 83-196900 disclose a resin binder for an antifouling paint composition having one metal ester structure in the polyester main chain. However, the metal ester bond of the binder has a remarkably high rate of abrasion in an aqueous alkaline solution such as seawater, so that it is difficult to maintain the coating film over a long period of time, and the molecular weight of the resin is small.

International Patent No. 91-1554 and U.S. Patent No. 5,199,977 disclose a technique for introducing non-volatile amines, alcohols, urea and phenol compounds as ligands in order to stabilize and lower the viscosity of the metal ester-containing binder structure . Examples of the amines to be used herein include rosin amines having 12 to 20 carbon atoms. When amine is applied as a ligand, the initial rate of wear can be controlled and the metal can be stabilized and lowered in concentration to the metal. However, these amines have a lower solubility in water than binders, resulting in a rapid decrease in the wear rate of the binder over time. In case of long-term exposure, cracks may occur in the seawater line. The ligands such as phenol, urea and alcohol described together are relatively poor in water resistance, which causes swelling, flaking and discoloration of the coating film.

Japanese Patent No. 2-196869 discloses a hydrolyzable copolymer composed of trimethylsilyl (meth) acrylate and a known unsaturated monomer. However, trimethylsilyl (meth) acrylate has been reported to have a degree of hydrolysis of about 70% as compared with conventional tin-based binders. This indicates that the hydrolysis degree of the salt in the metal ester structure is stronger than that of tin, It is judged that it is because it falls. Therefore, the content of hydrolyzed trimethylsilyl (meth) acrylate must be higher than that of other antifouling coating compositions. 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 substance having a small number of carbon atoms of an alkyl group bonded to silicon is added to improve the hydrolysis property, there is a problem that the long-term storage property is poor.

Korean Patent No. 97-700680 discloses a method of mixing a plastic (meth) acrylate copolymer in order to solve the problem of a copolymer composed of the trimethylsilyl (meth) acrylate monomer, but in this case, There is a problem that the abrasion rate gradually decreases as a large amount of non-hydrolyzable binder remains.

According to Japanese Patent No. 2010-150355, acrylic acid and methacrylic acid alone, acrylic acid and triisopropylacrylate mixed, and triisopropylacrylate alone are used as the hydrolysis elements, and antifouling coatings resistant to long-term wear and crack resistance Can be manufactured.

In WO09 / 031509, a metal salt bond-containing copolymer obtained by reacting (meth) acrylic acid with zinc or a copper compound was synthesized and radical polymerization was carried out together 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.

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. In the first step, acrylic acid-modified acrylic resin is prepared by copolymerizing an acrylic monomer including a (meth) acrylic acid monomer, and then reacted with a metal compound, a low molecular organic acid or the like to synthesize the final antifouling resin. The silyl type type can be produced by a conventional radical polymerization method since an acrylic monomer having an alkylsilyl pendant group having a hydrolyzable group is applied.

In the case of the hydrolyzable group of acrylic acid and triisopropylacrylate mixed together as in Japanese Patent Publication No. 2010-150355, it is prepared by a synthesis method similar to the non-saponification metal type process, and the silyl acrylate monomer is subjected to radical polymerization like the acrylic acid monomer, After the modified acrylic resin is prepared, it is reacted with a metal compound, a low molecular organic acid or the like to synthesize the final antifouling resin, which tends to be longer than the secondary synthesis time of the non-sapphire metallic type resin. The stoichiometric ratio in the secondary reaction of the acrylic acid-modified acrylic resin, the metal compound (divalent) and the low molecular organic acid is 1/1/1, that is, 2 moles of the acid and 1 mole of the metal compound react, In order to improve the whitening resistance and the like, there may be a case in which less than 2 moles of the acid is reacted with 1 mole of the metal compound. In this case, the second reaction time may be extended as compared with the conventional method.

An object of the present invention is to provide a resin for an antifouling paint having an improved color discoloration resistance and crack resistance by applying an organic acid containing a carboxylic acid group and an amine group and an antifouling paint composition containing the same.

In order to achieve the above object,

(A) a method for producing a polyester resin by a condensation reaction of an acrylic resin prepared by a radical reaction of a monomer containing a double bond and a carboxylic acid group with a monomer containing a double bond and an alkyl group, or a monomer containing an alcohol group and a monomer containing an acid group Polyester resin;

B) a divalent metal; And

C) a resin for an antifouling paint prepared by the condensation reaction of an organic acid containing a carboxylic acid group and an amine group.

The present invention also provides an antifouling paint composition comprising the resin for an antifouling paint according to the present invention as a binder component.

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

The For antifouling paints  Suzy

The resin for an antifouling paint of the present invention is produced by condensation reaction of component A, component B and component C. The condensation reaction can be carried out by a conventional method, and the solvent which can be used for the reaction is not particularly limited so long as it does not adversely affect the reaction, but aromatic hydrocarbon solvents such as toluene and xylene, methyl ethyl ketone, , Ketone solvents such as methyl butyl ketone, ethyl propyl ketone, methyl isobutyl ketone and methylaryl ketone, solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, isopropyl acetate, butyl acetate, methyl cellosolve acetate , Ester solvents such as cellosolve acetate, butyl cellosolve acetate and 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.

Component A: Acrylic resin or polyester resin

The acrylic resin according to the present invention is prepared by a radical reaction of a monomer containing a double bond and a carboxylic acid group and a monomer containing a double bond and an alkyl group.

The monomer containing a double bond and a carboxylic acid group is (meth) acrylic acid, or a monomer produced by a ring-opening reaction of a monomer containing a double bond and an alcohol group and an acid anhydride monomer.

Monomers containing a double bond and an alcohol group are C ₂ To C ₁₂ hydroxy alkyl (meth) acrylates, preferably 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxy isopropyl (meth) acrylate, butane Acrylate, diol mono (meth) acrylate, 4-hydroxybutyl (meth) acrylate and caprolactone (meth) acrylate.

The acid anhydride monomer is an aliphatic, alicyclic or aromatic acid anhydride of C ₁ to C ₂₄ , and is preferably an aliphatic, alicyclic or aromatic acid anhydride selected from the group consisting of succinic anhydride, maleic anhydride, dodecylsuccinic anhydride, octylsuccinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, (PMDA), 3,3 ', 4,4-oxydiphthalic dianhydride (ODPA), 3,3', 4,4'-tetramethyluronic anhydride, (4-aminobenzenesulfonic acid) dianhydride consisting of benzophenone tetracarboxylic dianhydride (BTDA), 4,4'-diphthalic acid (hexafluoroisopropylidene) anhydride (6FDA), benzoquinone tetracarboxylic dianhydride and ethylene tetracarboxylic dianhydride ≪ / RTI >

Monomers containing a double bond and an alkyl group may be used in combination with C ₁ to C ₁₂ alkyl (meth) acrylates, C ₃ to C ₁₂ cycloalkyl (meth) acrylates, and C ₆ to C _{12 C12} bicycloalkyl (meth) acrylate. ≪ / RTI > Preferable examples of the polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl Or more.

The polyester resin according to the present invention can be produced by the condensation reaction of a monomer containing an alcohol group and a monomer containing an acid group. Preferably, the monomer containing an alcohol group is C ₁ To C ₁₂ Aliphatic, alicyclic or aromatic alcohols having 1 to 6 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably aliphatic, alicyclic or aromatic alcohols, such as ethylene glycol, propylene glycol, trimethylolpropane, trimethylolethane, 1,6-hexanediol, diethylene glycol, , Triethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, ditrimethylolpropane, triethylolpropane, glycerin, pentaerythritol, 2- (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyisopropyl (meth) acrylate, butanediol mono ) Acrylate.

Monomers containing an acid group are C ₁ A group consisting of an aliphatic, alicyclic, aromatic acid of C ₂₄ and a group of C ₁ To C ₂₄ aliphatic, alicyclic and aromatic acid anhydrides, and preferably at least one selected from the group consisting of formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, succinic acid, malonic acid, , Stearic anhydride, maleic anhydride, dodecyl succinic anhydride, octyl succinic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, (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 3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-diphthalic acid (hexafluoroisopropylidene) anhydride (6FDA), benzoquinonetetracar Acids is at least one selected from the dianhydride, and ethylene tetracarboxylic acid dianhydride group consisting of water.

The acrylic resin by the radical reaction of the present invention or the polyester resin by the condensation reaction of the present invention can be produced by a conventional polymerization method of an acrylic monomer and a polymerization method of a polyester monomer. The solid content of the resin is preferably 10% or more and less than 90%, and the acid value (based on solid dispersion basis) is preferably 50 to 225 mg KOH / g. If the solid content is less than 10%, the abrasion resistance and discoloration resistance are deteriorated. If the solid content is more than 90%, the reaction temperature can not be controlled. If 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, have.

Component B: Divalent metal

The divalent metal used in the synthesis of the resin for an antifouling paint of the present invention has 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 +} , But is not limited thereto.

Component C: The carboxylic acid group Amine group  Containing organic acids

The organic acid containing a carboxylic acid group and an amine group can be prepared by reacting an amine with an anhydrous acid according to a known method and can also be prepared by a Michael reaction which is a reaction of an amine with a double bond.

Specifically, 1) an amine is reacted with an acid anhydride monomer, or 2) an amine is reacted with a monomer containing a double bond and a carboxylic acid group, or 3) an amine is reacted with a monomer containing a double bond and an alkyl group, Or 4) reacting an amine with a monomer containing a double bond and an alkyl group, a double bond and a monomer containing a carboxylic acid group.

Preferably, the amine of the present invention is C ₁ To C ₂₄ aliphatic amines, cycloaliphatic amines, or aromatic amines. More preferably, one of the group consisting of methylamine, dimethylamine, ethylamine, propylamine, butylamine, docylamine, triethylenetetramine, polyoxypropylenediamine, methylenebischloraniline, benzylamine and dimethylaminopropylamine Or more.

The acid anhydride monomer of the present invention may be selected from the group consisting of succinic anhydride, maleic anhydride, dodecylsuccinic anhydride, octylsuccinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, (PMDA), 3,3 ', 4,4-oxydiphthalic dianhydride (ODPA), 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA), 4,4 ' -Diphthalic acid (hexafluoroisopropylidene) anhydride (6FDA), benzoquinone tetracarboxylic dianhydride and ethylene tetracarboxylic acid dianhydride.

The monomers comprising a double bond and an alkyl group of the present invention are selected from the group consisting of C ₁ to C ₁₂ alkyl (meth) acrylates, C ₃ to C ₁₂ cycloalkyl (meth) acrylates and C ₆ to C ₁₂ bicycloalkyl ) Acrylate. ≪ / RTI > Preferable examples of the polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl Or more.

The monomer containing the double bond and the alcohol group of the present invention is a monomer having C ₂ To C ₁₂ hydroxy alkyl (meth) acrylates, preferably 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxy isopropyl (meth) acrylate, butane Acrylate, diol mono (meth) acrylate, 4-hydroxybutyl (meth) acrylate and caprolactone (meth) acrylate.

The monomer containing a double bond and a carboxylic acid group of the present invention is a monomer prepared by a ring-opening reaction of a monomer containing a double bond and an alcohol group and an acid anhydride monomer, and each monomer is as defined above.

Preferably, 1) an amine selected from C ₁ to C ₂₄ aliphatic, alicyclic or aromatic amines is reacted with an acid anhydride monomer, or 2) a C ₁ to C ₂₄ aliphatic, alicyclic or aromatic amine is selected Or 3) reacting an amine selected from C ₁ to C ₂₄ aliphatic, alicyclic or aromatic amines with a monomer having a double bond and an alkyl group, by reacting the amine with an amine having a double bond and a carboxylic acid group (I) an acid anhydride monomer or (ii) a monomer containing a double bond and a carboxylic acid group.

According to another aspect of the present invention, in addition to an organic acid containing a carboxylic acid group and an amine group, an organic acid used in producing a resin for an antifouling paint includes a carboxylic acid group and an amine group, The organic acid can be used in a weight ratio of 1: 9 to 9: 1. Examples of such low molecular organic acids include formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, succinic acid, malonic acid, oxalic acid, glutaric acid, adipic acid, And one or more selected from the group consisting of lauric acid, iglycolic acid, citric acid, phthalic acid, isophthalic acid, terephthalic acid, naphthenic acid and rosin.

The Antifouling paint  Composition

The antifouling paint composition of the present invention can be produced by using the resin for an antifouling paint of the present invention as a binder component, The antifouling component contained in the coating film comes out of the seawater and exhibits the 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, 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 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.

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.

Known antifouling agents in the form of organic or inorganic compounds as additives, pigments such as zinc oxide, which acts to improve the film strength, control the wear rate and coloring, antisagging agents, anti-settling agents, antifouling paints Various resins such as a plasticizer such as paraffin chloride, an acrylic resin, and a polyalkyl vinyl ether (vinyl ether (co) polymer) contributing to the improvement in crack resistance and a defoaming agent may 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 generally 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 improved in discoloration resistance and crack resistance by applying an organic acid containing a carboxylic acid group and an amine group to a resin for an antifouling paint, and an antifouling paint composition containing the same.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to those described in the following examples.

For antifouling paints  Preparation of Resin Component

Synthetic example  1: Preparation of component A

A thermometer and a condenser was charged with 300 g of butanol and 300 g of xylene 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 and 770 g of ethyl acrylate, 120 g of tertiary amyl peroxyhexanoate as initiator and 350 g of xylene was uniformly added dropwise over 4 hours and refluxed for 2 hours To obtain a transparent acrylic acid-modified acrylic resin having a solid content of 52.6%, a Gardner viscosity (25 ° C) of A1-A, and an acid value of 150 mg KOH / g (based on solid content of acrylic acid).

Synthetic example  2: Preparation of Component C

A thermometer and a condenser was charged with 172.0 g of dimethylaminopropylamine in a nitrogen atmosphere, and the temperature was raised to 90 ° C. Then, 168.4 g of ethyl acrylate was added dropwise for 30 minutes, and the mixture was maintained for 4 hours. After holding, 259.4 g of hexahydrophthalic anhydride was added dropwise for 30 minutes, and the resulting resin was maintained for 4 hours. The resin thus obtained was a transparent resin having a solid content of 100.0%, a Gardner viscosity (25 캜) Z7 and an acid value of 157 mg KOH / g.

Synthetic example  3: Preparation of Component C

A thermometer and a condenser was charged with 177.9 g of benzylamine in a nitrogen atmosphere, and the temperature was raised to 90 ° C. 166.1 g of ethyl acrylate was added dropwise thereto for 30 minutes and then maintained for 4 hours. After holding, 256.0 g of hexahydrophthalic anhydride was added dropwise for 30 minutes, and the resulting resin was maintained for 4 hours. The resin thus obtained was a clear resin having a solid content of 100.0%, a Gardner viscosity (25 캜) of Z7 + and an acid value of 155 mg KOH / g.

Synthetic example  4: Preparation of Component C

A thermometer and a condenser was charged with 113.5 g of dimethylaminopropylamine in a nitrogen atmosphere, and the temperature was raised to a reaction temperature of 90 ° C. 186.6 g of cyclohexyl methacrylate and 128.8 g of 2-hydroxyethyl acrylate were uniformly mixed, and the mixture was added dropwise for 30 minutes and then maintained for 4 hours. After holding, 171.2 g of hexahydrophthalic anhydride was added dropwise for 30 minutes, and the resulting resin was maintained for 4 hours. The resin thus obtained was a clear resin having a solid content of 100.0%, a Gardner viscosity (25 DEG C) Z9 and an acid value of 145 mg KOH / g.

For antifouling paints  Manufacture of resin

Example  One

A thermometer and a condenser, 207 g of Synthesis Example 1, 21.8 g of zinc oxide, 95.3 g of Synthesis Example 2, 63 g of xylene and 4.8 g of ionized water were charged and the temperature was raised to 100 캜 under a nitrogen atmosphere. The mixture was maintained at 100 DEG C for 5 hours to obtain a solid resin having a solid content of 55.3%, a Gardner viscosity (25 DEG C) Z, and a brown transparent resin.

Example  2

A thermometer and a condenser, 207 g of Synthesis Example 1, 21.8 g of zinc oxide, 96.63 g of Synthesis Example 3, 68 g of xylene, and 4.8 g of ionized water were charged and the temperature was raised to 100 캜 under a nitrogen atmosphere. The mixture was maintained at 100 DEG C for 5 hours to give a solid content of 55.3% and a Gardner viscosity (25 DEG C) Z1 < + >

Example  3

A thermometer and a condenser, 207 g of Synthesis Example 1, 21.8 g of zinc oxide, 103.3 g of Synthesis Example 4, 68 g of xylene and 4.8 g of ionized water were charged and the temperature was raised to 100 캜 under a nitrogen atmosphere. And maintained at 100 DEG C for 5 hours to obtain a solid resin having a solid content of 55.3%, a Gardner viscosity (25 DEG C) Z3, and a brown transparent resin.

Example  4

In a four-necked flask equipped with a thermometer and a condenser, 207 g of Synthesis Example 1, 21.8 g of zinc oxide, 51.6 g of Synthesis Example 4, 29.6 g of naphthenic acid, 53 g of xylene and 4.8 g of ionized water were charged under nitrogen atmosphere, Lt; / RTI > The mixture was maintained at 100 DEG C for 5 hours to give a solid content of 55.3%, a Gardner viscosity (25 DEG C) Z2, and a brown transparent resin.

Comparative Example  One

A thermometer and a condenser, 207 g of Synthesis Example 1, 21.8 g of zinc oxide, 59.1 g of naphthenic acid, 37.0 g of xylene, and 4.8 g of ionized water were charged and the temperature was raised to a reflux temperature of 100 占 폚. And maintained at 100 DEG C for 5 hours to obtain a solid content of 55.3%, a Gardner viscosity (25 DEG C) of Z2, and an orange transparent resin.

Antifouling paint  Preparation of the composition ( Example  5 to 8, Comparative Example  2)

An antifouling paint composition containing the above prepared Example 1, Example 2, Example 3, Example 4 and Comparative Example 1 as a binder component was prepared as shown in Table 1 and the physical properties were evaluated. The results are shown in Table 2 Respectively.

ingredient Example  5 Example  6 Example  7 Example  8 Comparative Example  2 bookbinder Example 1 27 Example 2 27 Example 3 27 Example 4 27 Comparative Example 1 27 Rojin ¹ 4 4 4 4 4 Plasticizer ² 2 2 2 2 2 Bengala ³ 5 5 5 5 5 Titan bag ⁴ 5 5 5 5 5 Talc ⁵ 10 10 10 10 10 Copper salt pyrithione ⁶ 5 5 5 5 5 Aliphatic amide wax ⁷ 2 2 2 2 2 Copper oxide ⁸ 25 25 25 25 25 Xylene ⁹ 15 15 15 15 30 Sum 100 100 100 100 100

Notes 1. Rosin: Gum Rosin [Jianxi sino native products]

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

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

4. Titanium bag: TIPAQUE CR-97 [Ishihara Sangyo Kaisha, Ltd.]

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

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

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

8. Copper ash: Red Copp 97N Premium [American Chemet]

9. Xylene: Xylene [SK corporation]

Properties Example  5 Example  6 Example  7 Example  8 Comparative Example  2 Paint solid 72.9 72.9 72.9 72.9 63.4 Paint viscosity 105 105 110 105 101 Press 5 5 5 5 5 Crack resistance 4 3 4 3 2 Antifouling performance 4 4 4 4 4 Wear rate 3.8 3.5 3.3 4.0 4.5 My discoloration property 4 5 5 3 2

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

5: Strain less than 3%

4: strain 3 ~ 5%

3: strain 5 ~ 7%

2: strain 7 to 10%

1: Strain more than 10%

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 test specimen.

3: 5 ~ 20% cracks of the total area of test specimen

2: 20 ~ 50% of the total area of test specimen cracked.

1: 50 ~ 70% of the total area of test specimen is cracked

0: More than 70% of the total area of the specimen is cracked.

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 vegetable contamination area is less than 20% of the effective area of the specimen

2: The condition that the vegetable contamination area is 20 to 50% of the effective area of the specimen

1: The condition that the vegetable contamination area is 50 ~ 100% of the effective area of the specimen

X: Animal contamination occurred

Measurement of wear rate

1) Specimen: 150 × 70 × 1 (mm) Stainless steel plate

2) Specimen treatment: epoxy-based paint 50 탆 → epoxy binder paint 50 탆 (each paint is dried and then dried at room temperature (20 캜) for 1 day)

3) Antifouling paint: 100 ㎛ After painting 1 week Dry at room temperature (20 ℃)

4) Test conditions: 12-month measurement by observing a rotary drum (600 mm × 300 mm), 25 knots,

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 determination - 14 days observation

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

From the results shown in Table 2, it was confirmed that the compositions for antifouling paint prepared in Examples 5 to 8 were much improved in discoloration resistance and crack resistance as compared with the composition for antifouling paint prepared in Comparative Example 2.

Claims (18)

A) an acrylic resin prepared by a radical reaction of a monomer containing a double bond and a carboxylic acid group and a monomer containing a double bond and an alkyl group;
B) a divalent metal; And
C) Resin for an antifouling paint prepared by the condensation reaction of an organic acid containing a carboxylic acid group and an amine group. The resin for an antifouling paint according to claim 1, wherein the acrylic resin has a solid content of 10% or more and less than 90% and an acid value based on a solid content basis of 50 to 225 mg KOH / g. The acrylic resin composition according to claim 1,
(Meth) acrylic acid, or a monomer prepared by a ring-opening reaction of a monomer containing a double bond and an alcohol group and an acid anhydride monomer,
Alkyl (meth) of C ₁ to C ₁₂ acrylates, C ₃ to C ₁₂ cycloalkyl (meth) acrylates and C ₆ to C ₁₂ in the bicyclo-alkyl (meth) at least one selected from the group consisting of acrylate and reaction By weight based on the total weight of the resin for an antifouling paint. The method of claim 3,
The monomer containing the double bond and the alcohol group is a C ₂ to C ₁₂ hydroxyalkyl (meth) acrylate,
Wherein said acid anhydride monomer is a C ₁ to C ₂₄ aliphatic, alicyclic or aromatic acid anhydride. delete The resin for an antifouling paint according to claim 1, wherein the bivalent metal is one selected from the group consisting of Zn ^{2 +} , Cu ^{2 +} , Mn ^{2 +} and Co ^{2 +} . 2. The method according to claim 1, wherein the organic acid containing carboxylic acid group and amine group is selected from the group consisting of
An aliphatic, alicyclic or aromatic amine of C ₁ to C ₂₄ with an acid anhydride monomer to produce a resin for an antifouling paint. 2. The method according to claim 1, wherein the organic acid containing carboxylic acid group and amine group is selected from the group consisting of
An aliphatic, alicyclic or aromatic amine of C ₁ to C ₂₄ with a monomer containing a double bond and a carboxylic acid group. 2. The method according to claim 1, wherein the organic acid containing carboxylic acid group and amine group is selected from the group consisting of
An aliphatic, alicyclic or aromatic amine of C ₁ to C ₂₄ is reacted with a monomer containing a double bond and an alkyl group and then reacted with an acid anhydride monomer or (ii) a monomer containing a double bond and a carboxylic acid group And then reacting the resultant resin with an antifouling paint. The method according to claim 1,
Characterized in that a resin for an antifouling paint is produced by further using a low-molecular organic acid at a weight ratio of 1: 9 to 9: 1 with respect to an organic acid containing a carboxylic acid group and an amine group. 11. The method of claim 10,
The low molecular organic acid may be at least one selected from the group consisting of formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, succinic acid, malonic acid, oxalic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, Wherein the resin is at least one selected from the group consisting of glycollic acid, citric acid, phthalic acid, isophthalic acid, terephthalic acid, naphthenic acid and rosin. 10. The method according to any one of claims 7 to 9,
The C ₁ to C ₂₄ aliphatic, alicyclic or aromatic amine may be selected from the group consisting of methylamine, dimethylamine, ethylamine, propylamine, butylamine, docylamine, triethylenetetramine, polyoxypropylenediamine, methylenebischloraniline, And dimethylaminopropylamine. ≪ RTI ID = 0.0 > 11. < / RTI > 10. The method according to claim 7 or 9,
The monomer containing the double bond and the alkyl group is preferably a monomer having at least one functional group selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl And at least one selected from the group consisting of
The acid anhydride monomers may be selected from the group consisting of succinic anhydride, maleic anhydride, dodecylsuccinic anhydride, octylsuccinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4-oxydiphthalic dianhydride (ODPA), 3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA) Wherein the antifouling paint is at least one selected from the group consisting of phthalic acid (hexafluoroisopropylidene) anhydride (6FDA), benzoquinonetetracarboxylic dianhydride, ethylene tetracarboxylic acid dianhydride and (meth) acrylic acid anhydride. Resin for. 9. The method of claim 8,
The monomer containing a double bond and a carboxylic acid group is prepared by a ring-opening reaction of a monomer containing a double bond and an alcohol group and an acid anhydride monomer,
Wherein the monomer containing the double bond and the alcohol group is a C ₂ to C ₁₂ hydroxyalkyl (meth) acrylate. An antifouling paint composition comprising the resin for an antifouling paint of claim 1 as a binder component. The antifouling paint composition according to claim 15, further comprising an antifouling agent and an antifouling agent elution regulator selected from the group consisting of rosin, a rosin derivative, a monocarboxylic acid or a salt thereof. The antifouling paint composition according to claim 16, wherein the antifouling agent elution controlling agent is contained in an amount of 0.1 to 25% by weight based on the total composition. The antifouling paint composition according to claim 16, further comprising at least one selected from the group consisting of a pigment, an anti-flow agent, an anti-settling agent, a plasticizer, a defoaming agent and a solvent.