KR20170049392A - Antifouling coating material composition and coated article having coating film - Google Patents

Abstract

The present invention aims to provide an antifouling paint composition and coated articles having a coating film of the antifouling paint composition, such as a fishing net, a ship, and a structure in the ocean or shore, capable of maintaining excellent antifouling properties for a long period of time, and forming an antifouling coating film on which a coating film defect, such as coating film detachment, blister, crack is hardly generated. The present invention relates to the antifouling paint composition comprising a polyester resin having a specific structural unit in a resin skeleton, a resin having a silyl ester group-containing resin and/or a metal carboxylate structure, and an antifouling agent, and also relates to the coated articles having the coating film of the composition.

Description

[0001] Antifouling coating composition and coated article having coating film [0002]

More particularly, the present invention relates to an antifouling paint composition capable of forming a antifouling coating film capable of maintaining an excellent antifouling property for a long period of time, and a coating film containing the antifouling paint composition The article relates to a coated article.

In recent years, as resins for antifouling paint replacing organotin-containing copolymers, which are susceptible to marine pollution, various resins having hydrolytic properties in seawater have been studied. When a coating film formed on the surface of a structure such as a ship which is in contact with seawater by using the antifouling coating composition (i.e., hydrolysis type antifouling coating composition) containing such a hydrolyzable resin is in contact with seawater, The decomposable resin gradually hydrolyzes to dissolve the coating film in the seawater, and the surface of the coating film is continuously updated, thereby making it possible to maintain its stain-preventing performance. As hydrolysis-resistant resins in sea water, hydrolysis-type antifouling coating compositions containing a trialkylsilyl ester group-containing resin or a resin having a metal carboxylate structure have been proposed so far. However, the trialkylsilyl ester group-containing resin has a different hydrolysis rate depending on the kind of the alkyl group possessed by the trialkylsilyl ester group and the structure of the resin, and the resin having a metal carboxylate structure has a different kind of metal, It is difficult to control the dissolution rate in the seawater of the obtained coating film in many cases because the anti-fouling paint composition using these resins having hydrolysable properties is often difficult.

Thus, a method of controlling the dissolution rate of a coating film by using a hydrolysis-type antifouling coating composition comprising a resin having such a hydrolyzable property and a rosin or rosin derivative has been studied (see Patent Documents 1 to 6). Although the dissolution rate of the coating film can be controlled to some extent by using the resin having hydrolyzable properties in combination with the rosin or rosin derivative, when the amount of the rosin or rosin derivative to be used is small, the solubility of the coating film in the seawater is sufficiently obtained And there is a problem that the performance of preventing the contamination of the coating film is difficult to continue. On the other hand, when the amount of the rosin or rosin derivative to be used is large, the dissolution rate of the coating film into the seawater is increased to improve the antifouling performance. However, since the physical properties and adhesion of the coating film are lowered, Coating film defects are liable to occur, and there is a possibility that long-term maintenance of the antifouling performance becomes difficult.

In order to solve these problems, anti-fouling paint compositions containing a polyester resin and a trialkylsilyl ester group-containing resin in a specific range of mass ratio have been proposed (see Patent Document 7). According to such an antifouling coating composition, it is possible to form a antifouling coating film which has excellent antifouling properties and is less likely to cause coating film defects such as blisters and cracks. However, depending on the sea area and coating composition of the antifouling coating film, There is a case that the coating performance is somewhat lacking in terms of long-term maintenance of the prevention performance, and therefore further improvement is demanded.

Patent Document 1: JP-A-10-30071 Patent Document 2: JP-A-2002-53797 Patent Document 3: JP-A-2011-26357 Patent Document 4: JP-A-2011-32489 Patent Document 5: International Publication No. 2011/046087 Patent Document 6: JP-A-9-286933 Patent Document 7: International Publication No. 2015/156073

An object of the present invention is to provide an antifouling paint composition capable of maintaining excellent antifouling properties over a long period of time and capable of forming a antifouling coating film in which coating film defects such as peeling of coating film, It is intended to provide a coated product such as a fishing net, a ship, a marine or coastal structure having a coated film of the coating composition.

The inventors of the present invention have conducted intensive studies in order to achieve the above object and have found that a polyester resin (A) having a specific structural unit in a resin skeleton and a resin having a silyl ester group-containing resin (B1) and / or a metal carboxylate structure B2) and the antifouling agent (C), it is possible to control the dissolution rate of the coating film into the oceans and to maintain excellent antifouling properties over a long period of time, It has been found that when the antifouling coating composition is applied to the bottom of a ship, coating film defects such as peeling of the coating film, blisters and cracks during traveling or during anchoring are less likely to occur. The present invention has been completed based on this knowledge.

The present invention provides the antifouling paint composition described in each of the following items, and a coated article having the coated film.

(Item 1) An antifouling paint composition comprising a polyester resin (A), a silyl ester group-containing resin (B1) and / or a resin having a metal carboxylate structure, and a antifouling agent (C) Wherein the polyester resin (A) has a constitutional unit represented by the following formula (1) in its resin skeleton and the total mass of the constitutional units is 2 to 50 mass%, based on the mass of the polyester resin (A) , And the mass ratio of the polyester resin (A) to the total of the silyl ester group-containing resin (B1) and the resin (B2) having a metal carboxylate structure is from 3/97 to 80/1, Lt; RTI ID = 0.0 > 20. ≪ / RTI >

[Chemical Formula 1]

(Wherein R ₀ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 100)

(Item 2) The resin composition according to item 2, wherein the silyl ester group-containing resin (B1) is at least one kind of monomer (b1) represented by the following formula (2), one or more kinds of the monomers (b2) The antifouling paint composition according to item 1, wherein the antifouling paint composition is a copolymer of two or more kinds of antifouling paints.

(2)

[Wherein, R ₄ represents a hydrogen atom or a methyl group, R _1, R ₂ and R ₃ each independently represent a hydrocarbon group, R ₅ is a hydrogen atom or R ₆ -O-CO- (However, R ₆ metaphor Or a silyl group represented by -SiR ₇ R ₈ R ₉ , and R ₇ , R ₈ and R ₉ each independently represent a hydrocarbon group.

(Item 3) The resin (B2) having the metal carboxylate structure has a characteristic group having a metal carboxylate structure represented by the following formula (3), wherein the resin (B2) having the metal carboxylate structure The antifouling paint composition according to item 1 or 2, wherein the content of the metal atom contained is within a range of 0.04 to 3.50 mol / Kg based on the solid content of the resin (B2).

(3)

(Wherein M represents a divalent metal atom and X represents at least one group selected from the group consisting of a hydroxyl group, an organic acid residue and an alcohol residue).

(Item 4) The polyester resin composition according to item 4, wherein the polyester resin (A) is a mixture of a raw material mixture containing at least one component selected from the group consisting of lactic acid, lactide and lactic acid lactic acid and glycolic acid, glycolide and polyglycolic acid , And the acid value of the polyester resin (A) is in the range of 0.1 to 120 KOH mg / g. The polyester resin (A) is a polyester resin prepared by using at least one raw material mixture of a raw material mixture containing at least one component selected from the group consisting of Wherein the antifouling coating composition is a coating composition comprising the antifouling coating composition according to any one of claims 1 to 3.

(Item 5) The antifouling paint composition according to any one of Items 1 to 4, wherein the polyester resin (A) has a weight average molecular weight of 190 to 15,000.

(Item 6) The antifouling paint composition according to any one of Items 1 to 5, wherein the polyester resin (A) has no metal carboxylate structure.

(Item 7) A coated article having a coating film of the antifouling paint composition according to any one of Items 1 to 6.

The antifouling paint composition of the present invention can maintain excellent antifouling properties for a long period of time and can form a coating film which is less prone to coating film defects such as peeling of coating film, blister, crack and the like.

The antifouling paint composition of the present invention is characterized by containing a resin (A), a silyl ester group-containing resin (B1) and / or a resin having a metal carboxylate structure (B2) Wherein the polyester resin (A) contains a structural unit represented by the following formula (1) in its resin skeleton, and the total mass of the structural units is in the range of from 1 to 20 parts by mass, based on the mass of the polyester resin (A) Wherein the mass ratio of the polyester resin (A) to the total of the silyl ester group-containing resin (B1) and the resin (B2) having a metal carboxylate structure is within a range of 2 to 50 mass% / 97 to 80/20.

[Chemical Formula 4]

(Wherein R ₀ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 100)

Hereinafter, the antifouling paint composition of the present invention will be described in detail.

[Polyester resin (A)]

The polyester resin (A) used in the antifouling paint composition of the present invention has the structural unit represented by the formula (1) in its resin skeleton. In order to introduce the structural unit represented by the formula (1) into the polyester resin, at least one component selected from the group consisting of lactic acid and lactic acid and lactic acid and glycolic acid, glycol It is preferable to use at least one component of at least one component selected from the group consisting of lead and polyglycolic acid as raw materials. In the present specification, the glycolide is also known as 1,4-dioxane-2,5-dione.

The total mass of the constituent unit represented by the above formula (1) is preferably from 2 to 50% by mass, more preferably from 2 to 50% by mass based on the mass of the polyester resin (A) when R ₀ in the formula (1) from 5 to 40 to% by mass, more preferably in the range of 10 to 30 mass%, in the case where R ₀ in the above formula (1) a hydrogen atom, by the mass of the polyester resin (a) as a reference, Is in the range of 2 to 50 mass%, preferably 4 to 40 mass%, and more preferably 6 to 30 mass%. When the total mass of the constituent units is less than 2% by mass or more than 50% by mass, it may be difficult to maintain the stain-proofing property of the obtained coating film for a long period of time.

The polyester resin (A) may be produced by a conventionally known method, and may be a mixture of at least one component selected from the group consisting of lactic acid and lactic acid lactic acid and glycolic acid, glycolide and polyglycolic acid (A1) other than glycolic acid, glycolide and polyglycolic acid, lactic acid and lactic acid of lactic acid and at least one component of at least one component selected from the group consisting of lactic acid, lactic acid and lactic acid of lactic acid, And polyol acid and an alcohol component (a2) other than glycolic acid, glycolide and polyglycolic acid, and reacting each of these components with each other.

On the other hand, the above reaction for producing the polyester resin (A) includes any of known reactions such as an esterification reaction, an ester exchange reaction, a ring-opening polymerization reaction, and a reaction at a ring-opening moiety. In the present specification, the above reaction for producing the polyester resin (A) may be referred to as a " polymerization reaction ".

Lactic and lactic Poly lactic acid

In the production of the polyester resin (A), lactide and lactic acid of lactic acid and lactic acid may be used as they are. These compounds each contain an optical isomer. In the present invention, those containing an L-form and a D-form at an arbitrary ratio can be used. In order to form an antifouling coating film which can maintain excellent antifouling properties over a long period of time and which is free from coating film defects such as peeling of coating film, blister, crack, etc., in the production of polyester resin (A) Of lactide and / or polylactic acid.

Glycolic acid , Glycolide  And Polyglycolic acid

In the production of the polyester resin (A), commercially available products such as glycolic acid, glycolide and polyglycolic acid may be used as they are. In order to form an antifouling coating film which can maintain excellent antifouling property over a long period of time and which is free from coating film defects such as peeling of coating films, blisters and cracks, in the production of polyester resin (A) Particular preference is given to using acids and / or glycolides.

In the production of the polyester resin (A), the above-mentioned poly (lactic acid) and poly (glycolic acid) can be used each having a weight average molecular weight in the range of 450 to 1,000,000.

The acid component (a1)

In the present invention, as the acid component (a1), an acid component generally used in the production of a polyester resin can be used. Examples of such acid components include alicyclic polybasic acids, aliphatic polybasic acids, aromatic polybasic acids, aromatic monocarboxylic acids, aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and esterified, anhydrides and halides of these acids have.

The alicyclic polybasic acid is generally a compound having at least one alicyclic structure (mainly a 4- to 6-membered ring) and at least two carboxyl groups in one molecule, and an acid anhydride, an esterified product, and a halide of the compound. Examples of the alicyclic polybasic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid Cyclohexene-1,2-dicarboxylic acid, tetrahydro-methylphthalic acid, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4- Alicyclic polycarboxylic acids such as methyl-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid and 1,3,5-cyclohexanetricarboxylic acid; Anhydrides of these alicyclic polyvalent carboxylic acids; And lower alkyl esters of these alicyclic polyvalent carboxylic acids. These may be used alone or in combination of two or more.

The aliphatic polybasic acid is generally an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, and a halide of the aliphatic compound. Examples of the aliphatic polybasic acid include aliphatic polybasic acids such as succinic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, , Aliphatic polycarboxylic acids such as octadecanedioic acid and citric acid; Anhydrides of these aliphatic polyvalent carboxylic acids; And halides of these aliphatic polycarboxylic acids. These may be used alone or in combination of two or more.

The aromatic polybasic acid is generally an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound, an esterified product of the aromatic compound, and a halogenated compound of an aromatic compound.

Examples of the aromatic polybasic acid having two carboxyl groups in one molecule include aromatic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid and 4,4'-biphenyldicarboxylic acid; And anhydrides of these aromatic polycarboxylic acids.

Examples of the aromatic polybasic acid having three or more carboxyl groups in one molecule include trivalent aromatic polycarboxylic acids and tetravalent aromatic polycarboxylic acids. Examples of trivalent aromatic polycarboxylic acids include trimellitic acids such as trimellitic acid, trimellitic anhydride, trimellitic acid alkyl ester and trimellitic acid halide; Hemimellitic acids such as hemimellitic acid, anhydrous hemimellitic acid, hemimellitic acid alkyl ester, and hemimellitic acid halide; Trimesic acids such as trimesic acid, trimesic acid alkyl ester, and trimesic acid halide; Various naphthalenetricarboxylic acids and their anhydrides having different positions of bonding of carboxyl groups to aromatic rings; Various anthracene tricarboxylic acids and their anhydrides having different positions of bonding of carboxyl groups to aromatic rings; Various biphenyltricarboxylic acids and their anhydrides having different positions of bonding of carboxyl groups to aromatic rings; Various benzophenonetricarboxylic acids and their anhydrides having different positions of bonding of carboxyl groups to aromatic rings; Ethylene bistrimelitic acid and anhydrides thereof. Examples of the tetravalent aromatic polycarboxylic acid include pyromellitic acids such as pyromellitic acid, pyrophyllitic acid dianhydride, pyromellitic acid alkyl ester and pyromellitic acid halide; Melphanic acid such as meloxic acid, melphanic acid dianhydride, melomatic acid alkyl ester, and melodic acid halide; Frenitic acids such as prehnitic acid, frenitic acid anhydride, furunitic acid alkyl ester, frenitic acid halide, and the like. The aromatic polybasic acid may be used alone or in combination of two or more.

In the present invention, as the acid component (a1) used in the production of the polyester resin (A), a monocarboxylic acid such as an aromatic monocarboxylic acid, an aliphatic monocarboxylic acid, or an alicyclic monocarboxylic acid may be used. Examples of the aromatic monocarboxylic acids include benzoic acid, methylbenzoic acid, ethylbenzoic acid, pt-butylbenzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, . Examples of the aliphatic monocarboxylic acid include acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, Fatty acids such as palmitoleic acid, oleic acid, erlidine acid, brassidic acid, linoleic acid, linolenic acid, rosin acid, palm oil fatty acid, cottonseed oil fatty acid, palm oil fatty acid, rice bran fatty acid, fatty fatty acid, tallow fatty acid, soybean fatty acid, linseed oil fatty acid, Saturated or unsaturated aliphatic monocarboxylic acids such as fatty acid, rapeseed fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, and new flower oil fatty acid. These may be used alone or in combination of two or more.

Examples of the alicyclic monocarboxylic acids include cyclohexanecarboxylic acid, cyclopentanecarboxylic acid, cycloheptanecarboxylic acid, 4-ethylcyclohexanecarboxylic acid, 4-hexylclohexanecarboxylic acid, 4-laurylcyclohexanecarboxylic acid, And the like. These may be used alone or in combination of two or more.

In the present invention, the acid component (a1) used in the production of the polyester resin (A) may contain an esterified product such as glycerin ester of the monocarboxylic acid. Examples of glycerin esters of monocarboxylic acids include palm oil, cottonseed oil, palm oil, rice bran oil, fish oil, tall oil, soybean oil, linseed oil, tung oil, rapeseed oil, castor oil, dehydrated castor oil, have.

In the present invention, the acid component (a1) used in the production of the polyester resin (A) preferably contains an aromatic polybasic acid in view of long-term maintenance of the antifouling property, is preferably not less than 30 mol%, preferably not less than 50 mol%, more preferably not less than 70 mol% based on the total molar amount of the repeating units (a1).

Alcohol component (a2)

In the present invention, as the alcohol component (a2), an alcohol component usually used in the production of a polyester resin may be used. The alcohol component preferably includes a dihydric alcohol such as an alicyclic diol, an aliphatic diol or an aromatic diol, and / or a polyhydric alcohol having a trivalent or higher valency, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, tri-1,2-propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1, 2-propylene glycol, Dihydroxycyclohexane, 3-ethoxypropane-1,2-diol, 3-phenoxypropane-1,2-diol, neopentyl glycol, 2-methyl- Propane diol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, 2,2- , 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-phenoxypropane- 1,3-diol, 1,3-propylene glycol, 1,3-butylene glycol, 2-ethyl-1,3-octanediol, 1,4-butanediol, 1,4-dihydroxycyclohexane, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 3-methyl- Pentanediol, 1,4-dimethyrolcyclohexane, tricyclodecane dimethanol, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate Bis (4-hydroxyhexyl) -2,2-propane, bis (4-hydroxyhexyl) methane, 3,9 Ester diol compounds such as bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and bis (hydroxyethyl) terephthalate, , Diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, mannit, trimethylol ethane, trimethylol propane, ditrimethylol propane, tris Roxy ethyl) iso Click rate, and the like polylactone polyol compound in addition to a lactone compound such as ε- caprolactone to these polyhydric alcohols, these may be used alone or in combination of two or more.

Further, if necessary, it may contain at least one alcohol selected from the group consisting of methanol, ethanol, propyl alcohol, n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, , Benzyl alcohol, stearyl alcohol, 2-phenoxyethanol, dodecyl alcohol, and other monoalcohols; An alcohol compound obtained by reacting a monoepoxy compound such as ethylene oxide, propylene oxide, butylene oxide, or a glycidyl ester of a synthetic high branched saturated fatty acid (trade name 'Cadilla E10' manufactured by HEXION Specialty Chemicals) with a compound having a protonic acid And the like can also be used as an auxiliary raw material in the production of the polyester resin (A).

In the present invention, the production method of the polyester resin (A) is not particularly limited and can be carried out according to a known method. The polyester resin (A) may contain at least one component selected from the group consisting of lactic acid, lactide and lactic acid, and at least one component selected from the group consisting of glycolic acid, glycolide and polyglycolic acid (A1) and at least one of the alcohol component (a2) in a nitrogen stream at a temperature of 150 to 250 占 폚 in an amount of 2 to 10 Time polymerization reaction. In the polymerization reaction, the order of the reaction of the raw materials may be arbitrarily adjusted. For example, lactide of lactic acid may be subjected to ring-opening polymerization reaction in advance to obtain polylactic acid, or glycolide may be subjected to ring- The acid component (a1) and the alcohol component (a2) may be subjected to a polymerization reaction in the presence of the ring-opening polymer. Also, by the polymerization reaction and / or the transesterification reaction of the polyester resin obtained by the polymerization reaction of the acid component (a1) and the alcohol component (a2) with the lactide or glycolide of the lactic acid, A) can be obtained. These reactions may be carried out in the presence of a known organic solvent.

The polymerization may be carried out using a catalyst in order to accelerate the reaction. Examples of such catalysts include dibutyltin oxide, antimony trioxide, iron acetate, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, acetic acid, tetrabutyl titanate, tetraisopropyl titanate, zinc borate, zinc chloride , Zinc sulfate, zinc naphthenate, zinc oxide, lead borate, lead acetate, manganese acetate, aluminum acetate, and aluminum chloride.

In the present invention, the polyester resin (A) preferably contains at least one component selected from lactic acid and lactic acid lactic acid and lactic acid, and at least one component selected from the group consisting of glycolic acid, glycolide and polyglycolic acid (A1) and the alcohol component (a2) in the presence of the acid component (a1) and the alcohol component (a2), by the polymerization reaction of at least one component of the component May contain a compound and / or an inorganic compound as a constituent component, and may be produced according to a known chemical reaction such as an amidation reaction, a urethanization reaction, an imidization reaction, a carbonation reaction, and an urea reaction. For example, the polyester resin (A) can be produced by reacting a reaction intermediate or a reaction product with a metal such as zinc oxide, organic acid copper, zinc chloride, zinc chloride, zinc hydroxide, copper hydroxide, zinc oxide, Or may be a modified polyester resin obtained by reacting with a compound, a fatty acid, a fat, a mono or polyisocyanate compound, a mono or polyamine compound having a nitrogen atom bonded thereto, an epoxy compound, an acrylic resin, a vinyl ester resin or the like. When at least one component selected from the group consisting of glycolic acid, glycolide and polyglycolic acid is used as a raw material, the polyester resin (A) may be lactic acid, lactic acid, The organic compound may also be included as a component other than the acid component (a1) and the alcohol component (a2).

On the other hand, the polyester resin (A) in the present invention may have a metal carboxylate structure. In that case, the polyester resin (A) may be included in the metal carboxylate structure based on the solid content of the polyester resin The content of the metal atom to be added is preferably lower than the content of the metal atom contained in the resin (B2) having a metal carboxylate structure described later, and is preferably less than 0.04 mol / Kg. Further, the polyester resin (A) And it is more preferable that it has substantially no metal carboxylate structure. When the polyester resin (A) has a metal carboxylate structure, the production cost of the antifouling paint composition using the resin may be increased.

When the antifouling coating composition of the present invention further contains a component (for example, a pigment component or a antifouling agent component) containing a metal compound, the antifouling paint composition may contain a metal The polyester resin (A) having substantially no carboxylate structure reacts with the above-mentioned component containing the metal compound to generate a metal carboxylate structure with time. The content of the metal atom contained in the metal carboxylate structure thus produced is preferably less than 1.5 mol / Kg based on the solid content of the polyester resin (A) from the viewpoint of storage stability of the antifouling paint composition , And more preferably less than 0.04 mol / Kg.

The polyester resin (A) contains at least one component selected from the group consisting of lactic acid and lactic acid lactic acid, and polylactic acid, and at least one component selected from the group consisting of glycolic acid, glycolide and polyglycolic acid The constituent components derived from the one component, the acid component (a1) and the alcohol component (a2) are preferably 80 mol% or more, more preferably 90 mol% or more of the total constituent components of the resin.

The resin acid value of the polyester resin (A) is preferably in the range of 0.1 to 120 mgKOH / g, more preferably in the range of 0.1 to 95 mgKOH / g in view of keeping the stain of the obtained coating film for a long period of time, And particularly preferably in the range of 0.3 to 50 mg KOH / g.

The weight average molecular weight of the polyester resin (A) is preferably within the range of 190 to 15000, more preferably within the range of 340 to 13000, in view of maintaining the stain- And more preferably in the range of 600 to 8000.

In the present specification, the weight average molecular weight is a value obtained by converting weight average molecular weight measured by gel permeation chromatography (manufactured by Tosoh Corporation, 'HLC8120GPC') based on weight average molecular weight of polystyrene. The weight average molecular weight was measured by using four columns (trade names: 'TSKgel G-4000H L', 'TSKgel G-3000H L', 'TSKgel G-2500H L' and 'TSKgel G- 2000H L' )), Mobile phase; Tetrahydrofuran, measurement temperature; 40 캜, flow rate; 1 mL / min, detector; RI conditions.

[Silyl ester group-containing resin (B1)]

The antifouling coating composition of the present invention further comprises a silyl ester group-containing resin (B1) and / or a resin (B2) having a metal carboxylate structure in addition to the polyester resin (A). The silyl ester group-containing resin (B1) can be obtained by copolymerizing a monomer (b1) having a polymerizable unsaturated group represented by the following general formula (2) and a trialkoxysilyl ester group-containing monomer (hereinafter sometimes referred to as "monomer (b1) (B2) having a polymerizable unsaturated group other than the monomer (b1), and preferably a copolymer of one or more species selected from the group consisting of a weight average molecular weight (Mw) of 1000 to 150000 , More preferably a copolymer having Mw in the range of 3000 to 80,000.

[Chemical Formula 5]

Wherein R ₄ represents a hydrogen atom or a methyl group, R ₁ , R ₂ and R ₃ each independently represent a hydrocarbon group, and R ₅ represents a hydrogen atom or R ₆ -O-CO- (provided that R ₆ represents an organic group or a silyl group represented by -SiR ₇ R ₈ R ₉ , and R ₇ , R ₈ and R ₉ each independently represent a hydrocarbon group.

When the Mw of the silyl ester group-containing resin (B1) used in the antifouling paint composition of the present invention is less than 1,000, the dissolution rate of the coating film obtained from the antifouling coating composition becomes large, but the physical properties of the coating film are deteriorated, Or the like may easily occur in some cases. When the Mw of the silyl ester group-containing resin (B1) exceeds 150000, the dissolution rate of the coating film obtained from the antifouling coating composition is lowered, and the antifouling property is sometimes lowered.

The monomer (b1) is represented by the following general formula (2-1) when R ₅ in the formula (2) is a hydrogen atom.

[Chemical Formula 6]

On the other hand, R _4, R _1, R ₂ and R ₃ in the formula (2-1) is, respectively is the same as R _4, R _1, R ₂ and R ₃ in sakgi formula (2).

The hydrocarbon group in R ₁ , R ₂ and R ₃ in the formula (2) or the formula (2-1) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, It is preferably a substituted or unsubstituted phenyl group, and the respective hydrocarbon groups may be the same or different. Among them, the hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group such as methyl, ethyl, propyl, n-butyl, s-butyl, t- desirable.

Examples of the monomer represented by the formula (2-1) (hereinafter referred to as "monomer (b1-1)") include trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, triisopropyl Trialkylsilyl (meth) acrylate such as trimethylsilyl (meth) acrylate, trimethylsilyl (meth) acrylate and the like. Among these, triisopropylsilyl (meth) acrylate is preferable from the viewpoints of the solubility of the coating film, the persistence of the antifouling performance, desirable.

The monomer (b1) is a monomer having a structure in which R ₅ in the formula (2) is 'R ₆ -O-CO-' (wherein R ₆ is an organic group or a silyl group represented by -SiR ₇ R ₈ R ₉ and R ₇ , R ₈ and R ₉ each independently represent a hydrocarbon group), represented by the following general formula (2-2).

(7)

On the other hand, R _4, R _1, R ₂ and R ₃ in the formula (2-2), are each the same as R _4, R _1, R ₂ and R ₃ in the formula (2).

Examples of the organic group represented by R ₆ in the formula (2) or the formula (2-2) include an alkyl group, a cycloalkyl group, an unsaturated alkyl group and an aralkyl group each having a straight or branched chain having 1 to 10 carbon atoms have.

Examples of the linear or branched alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, an n-butyl group, Butyl group, 2-methylbutyl group, 2-ethylbutyl group, pentyl group, 3-methylpentyl group, hexyl group, heptyl group and octyl group.

Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Examples of the unsaturated alkyl group include 2-propenyl group, 2-butenyl group, 3-butenyl group, 2-pentenyl group, 3-pentenyl group and 4-pentenyl group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, and a phenylpropyl group.

Meanwhile, the alkyl group, cycloalkyl group, unsaturated alkyl group and aralkyl group may have a substituent. Examples of such a substituent include an alkoxy group and an acyl group. The number of substituents, the position of substitution, and the like are not particularly limited as long as they do not interfere with the effect of the present invention.

Examples of the monomer represented by the formula (2-2) (hereinafter referred to as "monomer (b1-2)") include a maleic acid diester compound, a fumaric acid diester compound (wherein R ₄ in the formula (2-2) A hydrogen atom, etc.).

The hydrocarbon group in R ₇ , R ₈ and R ₉ in the formula (2) or the formula (2-2) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, And it is preferably a phenyl group which is chitained or unsubstituted, and each hydrocarbon group may be the same or different. Among them, the hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group such as methyl, ethyl, propyl, n-butyl, s-butyl, t-butyl or isopropyl .

The monomer (b1) is preferably an isopropylsilyl group-containing unsaturated monomer in view of the solubility of the obtained coating film, the persistence of the antifouling performance, and the difficulty of blister or crack generation. Examples of such isopropylsilyl group-containing unsaturated monomers include triisopropylsilyl (meth) acrylate, triisopropylsilyl 4-pentenoate, bis (triisopropylsilyl) maleate, methyltriisopropylsilyl maleate, Ethyl triisopropyl silyl, n-butyl triisopropyl silyl maleate, isobutyl triisopropyl silyl maleate, t-butyl triisopropyl silyl maleate, n-pentyl triisopropyl silyl maleate, isopentyl triisopropyl silyl maleate , 2-ethylhexyltriisopropylsilyl maleate, cyclohexyltriisopropylsilyl maleate, bis (triisopropylsilyl) fumarate, methyltriisopropylsilyl fumarate, ethyltriisopropylsilyl fumarate, n-butyl fumarate Triisopropylsilyl fumarate, isobutyltriisopropylsilyl fumarate, n-pentyltriisopropylsilyl fumarate, isopentyltriisobutyl fumarate Peel silyl, fumaric acid, 2-ethylhexyl triisopropylsilyl, fumaric acid and the like cyclohexyl triisopropylsilyl, Among these are preferred in particular (meth) acrylic acid triisopropylsilyl. These triisopropylsilyl group-containing monomers may be used alone or in combination of two or more.

The silyl ester group-containing resin (B1) is preferably obtained by copolymerizing the monomer (b1) and the monomer (b2) in a mass ratio (b1) / (b2) within a range of 20/80 to 70/30, (B1) / (b2) within the range of 30/70 to 60/40 in terms of mass ratio of the monomer (b1) and the monomer (b2).

When the mass ratio b1 / b2 of the monomer (b1) and the monomer (b2) is less than 20/80, the dissolution rate of the obtained coating film is slow, / (b2) is larger than 70/30, the solubility of the obtained coating film is increased, but it may be difficult to maintain the contamination-preventing effect for a long period of time.

Examples of the monomer (b2) copolymerizable with the monomer (b1) (or the monomers (b1-1) and / or (b1-2)) include methyl (meth) acrylate, ethyl (meth) (Meth) acrylic acid alkyls such as n-butyl acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and lauryl (meth) acrylate; (Meth) acrylic acid alkoxyalkyls such as 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; (Meth) acrylic acid ethylene glycol monomethyl, (meth) acrylate having a polyoxyethylene chain with one terminal of the molecule being an alkoxy group, (meth) acrylate having a polyoxypropylene chain having an alkoxy group at one terminal of the molecule, Alkylene glycol monomethyl (meth) acrylate such as glycol monomethyl; (Meth) acrylate of a monoester of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylic acid hydroxyalkyls such as caprolactone-modified products, aryl alcohols, and hydroxyl group-containing monomers such as (meth) acrylates having a polyoxyethylene chain having a hydroxyl group at the molecular terminal; (Meth) acrylonitrile, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N- Acrylamides, nitrogen-containing monomers such as adducts of glycidyl (meth) acrylate and amines; (Meth) acrylic acid esters such as benzyl (meth) acrylate and phenyl (meth) acrylate; Vinyl chloride; Vinylidene chloride; (Meth) acrylonitrile; Vinyl acetate; Butyl vinyl ether; Lauryl vinyl ether; N-vinylpyrrolidone; Styrene; Vinyl toluene; ? -methylstyrene and the like.

Examples of the monomer (b2) include vinyl ester compounds such as vinyl propionate and vinyl acetate; Carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, crotonic acid, and (meth) acrylic acid? -Carboxyethyl; Epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3-methylcyclohexylmethyl (meth) acrylate, , Epoxy group-containing monomers such as 4-epoxycyclohexylpropyl (meth) acrylate and aryl glycidyl ether; Sulfonic acid group-containing monomers such as 2- (meth) acrylamide-2-methylpropanesulfonic acid, arylsulfonic acid, styrenesulfonic acid, sulfoethyl (meth) acrylate and their sodium or ammonium salts; Monomers having a phosphate group such as 2- (meth) acryloyloxyethyl acid phosphate; (Meth) acrylates such as acrolein, diacetone (meth) acrylamide, acetacetoxyethyl (meth) acrylate, vinyl alkyl ketones having 4 to 7 carbon atoms (e.g., vinyl methyl ketone, vinyl ethyl ketone and vinyl butyl ketone) Carbonyl group-containing monomers, and the like.

The monomers (b2) exemplified above may be used alone or in combination of two or more. Of the monomers (b2) exemplified above, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl Methoxyethyl (meth) acrylate, and 2-methoxypropyl (meth) acrylate.

In the present specification, '(meth) acrylate' means acrylate or methacrylate, and '(meth) acrylic acid' means acrylic acid or methacrylic acid. In addition, '(meth) acryloyl' means acryloyl or methacryloyl, and '(meth) acrylamide' means acrylamide or methacrylamide.

In the present invention, the silyl ester group-containing resin (B1) can be produced by a known polymerization method. On the other hand, the silyl ester group-containing resin (B1) may be any type of copolymer as long as it is a known copolymer such as a random copolymer, a graft copolymer, an oblique structural copolymer or a block copolymer.

The silyl ester group-containing resin (B1) can be obtained, for example, by copolymerizing the monomer (b1) and the monomer (b2) in the presence of a radical polymerization initiator.

Examples of the radical polymerization initiator used in the copolymerization reaction include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, dimethyl-2,2 Azo compounds such as azobisisobutylate; Diacyl peroxide compounds such as dibenzoyl peroxide, di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, and dilauryl peroxide; T-butyl peroxide compounds such as di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, and t-butyl peroctoate; t-amyl peroxyacetate, t-amyl peroxy-2-ethyl hexanoate, t-amyl peroxyacetate, t-amyl peroxyisonanoate, t- Oxides), 1,1-di (t-amylperoxy) cyclohexane, and other t-amyl peroxide compounds; t-hexylperoxy-2-ethylhexanoate, t-hexylperoxybenzoate, t-hexylperoxy-isopropyl monocarbonate, t-hexylperoxy pivalate, t-hexylperoxy neodecanoate, etc. And t-hexylperoxide compounds such as t-hexylperoxide compounds. These polymerization initiators may be used alone or in combination of two or more.

The molecular weight of the silyl ester group-containing resin (B1) can be adjusted by appropriately setting the amount of the polymerization initiator and the like.

Examples of the polymerization method for obtaining the silyl ester group-containing resin (B1) include a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, and a suspension polymerization method. Among them, the solution polymerization method is particularly preferable because the silyl ester group-containing resin (B1) can be synthesized easily and precisely.

In the copolymerization reaction, an organic solvent may be used if necessary. Examples of such organic solvents include aromatic hydrocarbon solvents such as xylene and toluene; Aliphatic hydrocarbon solvents such as hexane and heptane; Ester solvents such as ethyl acetate, butyl acetate, isopropyl butyrate and methoxypropyl acetate; Alcohol solvents such as isopropyl alcohol and butyl alcohol; Ether solvents such as dioxane, diethyl ether and dibutyl ether; And ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Of these, aromatic hydrocarbon solvents are preferable, and xylene is particularly preferable. These solvents may be used alone or in combination of two or more.

The reaction temperature in the copolymerization reaction may be appropriately set according to the kind of the polymerization initiator and the like, and is usually a temperature within the range of 70 to 160 ° C, preferably within the range of 80 to 140 ° C. The reaction time in the copolymerization reaction may be suitably set in accordance with the reaction temperature, the kind of the polymerization initiator, and the like, and is usually about 4 to 8 hours. The copolymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.

[Resin (B2) having a metal carboxylate structure]

The antifouling paint composition of the present invention may contain, in place of the silyl ester group-containing resin (B1) or the silyl ester group-containing resin (B1), a resin (B2) having a metal carboxylate structure , And the resin (B2) having the metal carboxylate structure may be simply referred to as " resin (B2) "). If the resin (B2) is a resin having a metal carboxylate structure, known resins can be used without being limited to the type and composition of the resin.

The resin (B2) includes a characteristic group having a metal carboxylate structure represented by the following general formula (3).

[Chemical Formula 8]

(Wherein M represents a divalent metal atom and X represents at least one group selected from the group consisting of a hydroxyl group, an organic acid residue and an alcohol residue).

Examples of the divalent metal atom (M) in the formula (3) include metal atoms such as zinc, copper, magnesium, calcium, iron and terel, have.

The resin (B2) containing the characteristic group (bb1) having a metal carboxylate structure in which X in the formula (3) is a hydroxyl group can be obtained, for example, by reacting a known resin having a carboxyl group with 1 mole of a carboxyl group In the presence of water, of an oxide or a divalent metal oxide in an amount within a range of 0.1 to 1.0 mol based on the weight of the metal oxide. The amount of water to be used in such a reaction is preferably in the range of 0.1 to 10.0 moles relative to 1 mole of the carboxyl group. If the amount of such water is less than 0.1 mol, the structural viscosity tends to be large, and handling of the resulting resin (B2) having a metal carboxylate structure may become difficult. On the other hand, if the amount of water used exceeds 10.0 moles, it may be necessary to separate the excess water.

As a concrete production method of the resin (B2) including the characteristic group (bb1), for example, a resin having a carboxyl group, water, and a divalent metal compound are placed in a reaction vessel and heated at a temperature of 50 ° C to 150 ° C And the reaction is carried out for 1 to 20 hours. The reaction may be carried out by adding an appropriate organic solvent to the reaction vessel. Examples of such organic solvents include alcohol solvents, ketone solvents, ester solvents and ether solvents. These solvents may be used singly or in combination of two or more.

The bivalent metal compound used in the production of the resin (B2) including the characteristic group (bb1) can be any known one without particular limitation, and copper, zinc, calcium , Magnesium, iron and terel, and zinc, or a copper oxide, a salt or a hydroxide, is more preferable.

As the resin having a carboxyl group used for the production of the resin (B2) including the characteristic group (bb1), for example, a resin such as a vinyl polymer, polyester, polyurethane, natural resin, A vinyl polymer obtained by copolymerizing a carboxyl group-containing unsaturated monomer such as (meth) acrylic acid, maleic acid, fumaric acid or itaconic acid with another unsaturated monomer such as alkyl (meth) acrylate or styrene is suitably used Can be used.

As the resin (B2) containing the characteristic group (bb2) having a metal carboxylate structure in which X in the formula (3) is an organic acid residue, for example, an unsaturated monomer containing the characteristic group (bb2) (bb2m) and at least one unsaturated monomer (m1) other than the unsaturated monomer (bb2m) and at least one unsaturated monomer (m1) other than the unsaturated monomer (bb2m) A copolymer obtained by modifying the copolymer by any method, or an arbitrary resin modified by the copolymer.

Examples of the unsaturated monomer (bb2m) include those represented by the following general formula (4) or (5).

[Chemical Formula 9]

[Chemical formula 10]

In the formula (4) or (5), R ₁₀ , R ₁₁ and R ₁₂ represent a hydrogen atom or a methyl group, A represents an organic acid residue, and M represents a divalent metal atom.

Examples of the method for producing the unsaturated monomer (bb2m-1) represented by the formula (4) in the unsaturated monomer (bb2m) include a method in which a polymerizable unsaturated organic acid such as (meth) acrylic acid, an oxide of a divalent metal, A method of reacting a metal compound such as a salt with a monobasic organic acid capable of forming an organic acid residue, a method of reacting a polymerizable unsaturated organic acid with a metal salt of a monobasic organic acid, and the like. These reactions may be carried out in the presence of an organic solvent and / or water as required.

Examples of the unsaturated monomer (bb2m-2) represented by the formula (5) in the unsaturated monomer (bb2m) include a polymerizable unsaturated organic acid such as (meth) acrylic acid, an oxide of a divalent metal, And a method in which a metal compound such as a salt is reacted. The reaction may be carried out in the presence of an organic solvent and / or water, if necessary.

When X in the formula (3) is an organic acid residue, examples of the organic acid residue include acetic acid, monochloroacetic acid, monofluoroacetic acid, naphthenic acid, propionic acid, capronic acid, caprylic acid, Naphthoic acid, erucic acid, erucic acid, linoleic acid, linoleic acid, stearic acid, ricinoleic acid, ricinoleic acid, erucic acid, erucic acid, Naphthoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinolinecarboxylic acid, nitrobenzoic acid, nitronaphthalenecarboxylic acid, But are not limited to, lactic acid, lactic acid, tartaric acid, lactic acid, lactic acid, lactic acid, lactic acid, lactic acid, , Isopimarane, and compounds having a labyrinth skeleton. It includes those derived from. The organic acid residue represented by A in the formula (4) may also be derived from the above organic acid.

Specific examples of the unsaturated monomer (bb2m-1) include, for example, acrylic acid esters such as magnesium acetate (meth) acrylate, zinc acetate (meth) acrylate, zinc naphthenate (meth) acrylate, (Meth) acrylate, monochloroacetic acid magnesium (meth) acrylate, monochloroacetic acid magnesium (meth) acrylate, monochloroacetic acid zinc (meth) (Meth) acrylate, magnesium caproate (meth) acrylate, zinc caproate (meth) acrylate, monofluoroacetic acid (meth) acrylate, magnesium propionate (Meth) acrylate, caproic acid (meth) acrylate, magnesium caprylate (meth) acrylate, zinc (meth) acrylate caprylate (Meth) acrylate, 2-ethylhexyl acrylate (meth) acrylate, 2-ethylhexyl acrylate (meth) acrylate, caprylic acid (Meth) acrylate, caprylic acid (meth) acrylate, caprylic acid zinc (meth) acrylate, caprylic acid (meth) acrylate, magnesium versatate (Meth) acrylate, zinc (meth) acrylate, zinc stearate (meth) acrylate, magnesium stearate, magnesium stearate, (Meth) acrylate, cresentine (meth) acrylate, magnesium cresat (meth) acrylate, magnesium cresate (meth) acrylate, (Meth) acrylate, zinc stearate (meth) acrylate, magnesium oleate (meth) acrylate, magnesium laurate (meth) acrylate, zinc laurate (Meth) acrylate, linolenic acid copper (meth) acrylate, linolenic acid copper (meth) acrylate, linolenic acid copper (meth) acrylate, magnesium linolenate Acrylate, ricinoleic acid zinc (meth) acrylate, ricinoleic acid (meth) acrylate, zinc stearate (meth) acrylate, stearoyl (meth) acrylate, (Meth) acrylate, zinc ricinoleate laurate (meth) acrylate, ricinoleylidene magnesium (meth) acrylate, (Meth) acrylate, zinc brassidate (meth) acrylate, brassidic acid scandium (meth) acrylate, magnesium erglucose (meth) acrylate, zinc erucate (meth) (Meth) acrylate,? -Naphthoic acid magnesium (meth) acrylate,? -Naphthoic acid zinc (meth) acrylate,? (Meth) acrylate, zinc benzoate (meth) acrylate, zinc benzoate (meth) acrylate, zinc benzoate (metha) acrylate, (Meth) acrylate, 2,4,5-trichlorophenoxyacetic acid magnesium (meth) acrylate, 2,4,5-trichlorophenoxyacetic acid zinc (meth) acrylate, 2,4,5- (Meth) acrylate, 2,4-dichlorophenoxyacetic acid (meth) acrylate Acrylate, 2,4-dichlorophenoxyacetic acid zinc (meth) acrylate, 2,4-dichlorophenoxyacetic acid (meth) acrylate, quinolinecarboxylic acid magnesium (meth) acrylate, zinc quinolinecarboxylate (Meth) acrylate, nitrobenzoic acid zinc (meth) acrylate, nitrobenzoic acid copper (meth) acrylate, nitronaphthalenecarboxylic acid magnesium (meth) acrylate, (Meth) acrylate, naphthalenecarboxylic acid zinc (meth) acrylate, nitronaphthalenecarboxylic acid (meth) acrylate, magnesium stearate (metha) acrylate, zinc stearate . These unsaturated monomers (bb2m-1) may be used singly or in a combination of two or more, if necessary.

As the unsaturated monomer (bb2m-2) represented by the formula (5), such as acrylic acid magnesium ((CH ₂ = CHCOO), ₂ Mg), methacrylic acid, the magnesium ((CH ₂ = C (CH _3), COO) ₂ Mg ) acrylate, zinc _{((CH 2 = CHCOO) 2} Zn), zinc methacrylate _{((CH 2 = C (CH} 3) COO) 2 Zn), acrylic Shandong _{((CH 2 = CHCOO) 2} Cu), methacrylonitrile (CH ₂ ═C (CH ₃ ) COO) ₂ Cu), and the like. These unsaturated monomers (b2m-2) may be appropriately selected and used as needed. Among these unsaturated monomers, from the viewpoint of maintaining the antifouling performance of the resulting coating film for a long period of time, zinc (meth) Is preferably used.

The amount of the unsaturated monomer (bb2m-1) used for obtaining the resin (B2) containing the characteristic group (bb2) is preferably from 1 to 50 parts by weight, Is preferably within a range of 0.5 to 30.0 mass%, and more preferably within a range of 1.0 to 20.0 mass%.

The amount of the unsaturated monomer (bb2m-2) used for obtaining the resin (B2) containing the characteristic group (bb2) is preferably from 1 to 50 parts by weight, Is preferably in the range of 0.5 to 50.0 mass%, more preferably 1.0 to 30.0 mass%, based on the solid mass.

As the resin (B2) containing the characteristic group (b3) having a metal carboxylate structure in which X in the formula (3) is an alcohol residue, for example, an unsaturated monomer (b3m) containing the characteristic group (b3) (B3m) and at least one unsaturated monomer (m2) other than the unsaturated monomer (b3m), wherein at least one of the unsaturated monomers (b3m) and (b3m) , Resins obtained by modifying the copolymer by any method, or resins modified by the copolymer.

Examples of the method for producing the unsaturated monomer (b3m) include a method in which a polymerizable unsaturated organic acid such as (meth) acrylic acid, a metal compound such as an oxide, a hydroxide, or a salt of a divalent metal and an alcohol capable of forming an alcohol residue , A method of reacting a polymerizable unsaturated organic acid with a metal alkoxide compound, and the like. These reactions may be carried out in the presence of an organic solvent and / or water as required.

The resin (B2) may further contain at least one kind of unsaturated monomer selected from the group consisting of the unsaturated monomers (bb2m-1), (bb2m-2) and (b3m) and, if necessary, other unsaturated monomers m < 3 >).

The unsaturated monomers (m1), (m2) and (m3) may be the same or different. Examples of the unsaturated monomers (m1), (m2) and (m3) include those exemplified as the monomers (b2) usable in the production of the silyl ester group-containing resin (B1).

The copolymerization reaction including the unsaturated monomer (bb2m) and / or (b3m) can be carried out, for example, in the presence of a radical polymerization initiator. As the radical polymerization initiator, those which can be used for the copolymerization reaction of the monomer (b1) and the monomer (b2) in the production of the silyl ester group-containing resin (B1) can be used.

The resin (B2) can be obtained, for example, by mixing a known resin having a carboxyl group with a metal compound such as an oxide or hydroxide of a divalent metal in an amount within a range of 0.1 to 1.0 mol based on 1 mol of the carboxyl group in the resin , And optionally, an organic acid, an alcohol compound or water at a temperature of 50 to 200 캜 for 1 to 20 hours. X in the characteristic group having the metal carboxylate structure represented by the formula (3) contained in the resin (B2) produced by this reaction is at least one kind selected from the group consisting of a hydroxyl group, an organic acid residue and an alcohol residue , And the composition ratio thereof is not particularly limited. This reaction may be carried out in the presence of a suitable organic solvent. Examples of the organic solvent in this case include alcoholic, ketonic, esteric, and etheric solvents. These can be used in combination.

The bivalent metal compound used in the production of the resin (B2) may be any known one without particular limitation, and it is preferable that the bivalent metal compound is a compound of zinc, copper, magnesium, calcium, iron and terel in terms of cost, toxicity, An oxide, a salt or a hydroxide of at least one metal selected from the group consisting of zinc and copper is more preferable, and zinc or copper oxide, salt or hydroxide is more preferable.

As the resin having a carboxyl group used for the production of the resin (B2), for example, a resin such as a vinyl polymer, polyester, polyurethane, natural resin and the like can be used. A vinyl polymer obtained by copolymerizing a carboxyl group-containing unsaturated monomer such as acrylic acid, maleic acid, fumaric acid or itaconic acid with another unsaturated monomer such as alkyl (meth) acrylate or styrene may be suitably used.

The resin (B2) containing the characteristic group (bb2) may be produced by reacting a known resin having a carboxyl group with a divalent metal salt of a monobasic organic acid.

In the present invention, X in the characteristic group having a metal carboxylate structure represented by the above general formula (3) contained in the resin (B2) having a metal carboxylate structure is preferably an integer of from 1 to 10, , And the content of the metal atom contained in the metal carboxylate structure is in the range of 0.04 to 3.50 mol / Kg based on the solid content of the resin (B2) , Preferably in the range of 0.07 to 3.00 mol / Kg, and more preferably in the range of 0.10 to 2.50 mol / Kg. If the content of the metal atom is more than 3.50 mol / Kg, the preservation period of the antifouling property of the obtained coating film may be shortened, and if it is less than 0.04 mol / Kg, the antifouling property of the obtained coating film tends to be lowered.

As other production methods of the resin (B2) having a metal carboxylate structure, for example, a condensation reaction of a compound having two or more carboxyl groups in one molecule with a metal compound, a polyol compound having a metal carboxylate structure A mid-portion reaction or a condensation reaction.

[Antifouling Agent (C)]

The antifouling paint composition of the present invention further comprises a antifouling agent (C) in addition to the polyester resin (A), the silyl ester group-containing resin (B1) and / or the resin having a metal carboxylate structure (B2) do. As the antifouling agent (C), conventionally known ones can be used, and examples thereof include an inorganic compound, an organic compound containing a metal, and an organic compound containing no metal.

Examples of the inorganic compound include copper compounds such as zinc rosin powder, copper powder, copper thiocyanate, carbonic acid copper, copper chloride and copper sulfate, zinc compounds such as zinc sulfate and zinc oxide, nickel compounds such as nickel sulfate and copper- .

As the organic compound containing a metal, for example, an organic copper compound, an organic nickel compound, an organic zinc compound and the like can be used. In addition, mannev, mansever, propyne and the like can also be used. Examples of the organic copper compound include oxydine, copper phthalocyanine, nonylphenolsulfonic acid copper, copper (ethylenediamine) -bis (dodecylbenzenesulfonate), acetic acid, naphthenic acid, bis Acid) copper and the like. Examples of the organic nickel compound include nickel acetate, nickel dimethyldithiocarbamate, and the like. Examples of the organic zinc-based compound include zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, zinc pyrithione, and ethylene bisdithiocarbamate zinc.

Examples of the organic compound not containing the metal include N-trihalomethyl thioetherimide, dithiocarbamic acid, N-aryl maleimide, 3-substituted amino-1,3-thiazolidin- 2,4-dione, dithiocyano-based compounds, triazine-based compounds, and the like.

Examples of the N-trihalomethyl thioetherimide include N-trichloromethyl thioetherimide and N-fluorodichloromethyl thioetherimide.

Examples of the dithiocarbamic acid include bis (dimethylthiocarbamoyl) disulfide, ammonium N-methyldithiocarbamate, ethylene bis (dithiocarbamate) ammonium, and wheat nev.

Examples of the N-aryl maleimide include N- (2,4,6-trichlorophenyl) maleimide, N-4-trimaleimide, N-3-chlorophenylmaleimide, N- (2 ', 6'-diethylphenyl) maleimide, N- (2,3-cyclohexylmaleimide) Amide, 2,3-dichloro-N- (2'-ethyl-6'-methylphenyl) maleimide and the like.

Examples of the 3-substituted amino-1,3-thiazolidin-2,4-dione include 3-benzylideneamino-1,3-thiazolidin-2,4-dione, 3- (4- Thiazolidin-2,4-dione, 3- (4-hydroxybenzylideneamino) -1,3-thiazolidin- -Dimethylaminobenzylideneamino) -1,3-thiazolidin-2,4-dione, 3- (2,4-dichlorobenzylideneamino) -1,3-thiazolidin- .

Examples of the dithiocyano-based compound include dithiocyanomethane, dithiocyanoethane, and 2,5-dithioanthiophene.

Examples of the triazine compound include 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine and the like.

In addition to the organic compounds exemplified above, examples of the organic compound containing no metal include 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenyl element, 4,5- N-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfonamide, tetramethylthiuram disulfide, 3-iodo- (Methoxycarbonylamino) benzoimidazole, 2,3,5,6-tetrachloro-4- (methanesulfonyl) pyridine, diiodomethylparatrisulfone, bisdimethyldithi Bis (4-thiazolyl) benzimidazole, triphenylboron pyridine-amine complex, medetomidine (system name: (± Fluoro-N- (p-tolyl) methane sulfenamide, 2- (2-methoxyphenyl) (p-claw Phenyl) -3-cyano and the like can be mentioned 4-bromo-5-trifluoromethyl pyrrole, chloromethyl -n- octyl disulfide.

As the antifouling agent (C), each of the compounds exemplified above may be used alone or in combination of two or more. The antifouling agent (C) is preferably used from the standpoint of exhibiting stable antifouling performance among the compounds exemplified above, and it is particularly preferable to use antifouling and copper rich onion.

[Antifouling paint composition and painted article having the coating film]

The antifouling paint composition of the present invention is characterized by containing a resin (A), a silyl ester group-containing resin (B1) and / or a resin having a metal carboxylate structure (B2) Wherein the polyester resin (A) has a structural unit represented by the formula (1) in its resin skeleton, and the polyester resin (A), the silyl ester group-containing resin (B1) and the metal carboxylate And the resin (B2) having a rate structure is in the range of 3/97 to 80/20.

The mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B1) and / or the resin (B2) having a metal carboxylate structure is in the range of 3/97 to 80/20, Is in the range of 7/93 to 60/40, and more preferably in the range of 10/90 to 40/60. When the mass ratio is in the range of 3/97 to 80/20, the excellent antifouling performance of the antifouling coating film obtained by the antifouling coating composition of the present invention can be maintained for a long period of time. Further, in the antifouling coating film, Coating film defects such as peeling, blister, and cracks are less likely to occur. When the mass ratio is less than 3/97 or larger than 80/20, it may be difficult to maintain the obtained antifouling performance of the coated film for a long period of time.

The mass ratio of the silyl ester group-containing resin (B1) to the resin (B2) having a metal carboxylate structure in the coating composition of the present invention can be used within a range of from 0/100 to 100/0.

In the antifouling paint composition of the present invention, the content of the antifouling agent (C) is preferably such that the content of the antifouling agent (C) in the polyester resin (A), the silyl ester group-containing resin (B1) and the resin having a metal carboxylate structure Is in the range of 50 to 500 mass%, preferably 250 to 400 mass%, based on the total mass. If the content of the antifouling agent (C) is less than 50% by mass, it may be difficult to maintain the antifouling performance of the obtained coating film for a long period of time. When the content of the antifouling agent (C) is more than 500% , The physical properties of the resultant coating film may deteriorate and defects such as peeling and swelling may occur.

The antifouling paint composition of the present invention may further contain a pigment, a dye (C), an antioxidant (C), a polyester resin (A), a silyl ester group-containing resin (B1) and / or a metal carboxylate structure- , Dehydrating agents, plasticizers, stabilizers (flow inhibitors), antifoaming agents and antioxidants; A resin other than the polyester resin (A), the silyl ester group-containing resin (B1) and the resin having a metal carboxylate structure (B2); Organic acids; Various kinds of components used in a general coating composition such as a solvent can be blended if necessary. These components may be used alone or in combination of two or more.

Examples of the pigment include coloring pigments such as spinel, talc, titanium oxide, yellow iron oxide, silica, calcium carbonate, barium sulfate, calcium oxide, carbon black, naphthol red, phthalocyanine blue, talc, silica, mica, And extender pigments such as calcium, kaolin, alumina white, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate and zinc sulfate.

The content of the pigment in the antifouling coating composition of the present invention is preferably from 1 to 50 parts by weight based on the total mass of the polyester resin (A), the resin (B1) having a silyl ester group and the resin (B2) having a metal carboxylate structure, But is preferably in the range of 0.05 to 1000 mass%, more preferably in the range of 1 to 500 mass%.

The dehydrating agent is a component contributing to improvement of the storage stability of the antifouling coating composition. Examples of such dehydrating agents include inorganic gypsum, anhydrous gypsum, semi-gypsum and synthetic zeolite-based adsorbents (for example, "Molecular sieve" (trade name)). (For example, methyl orthoformate, methyl orthoacetate, orthoboric acid ester, etc.), silicates, isocyanates, and the like. Among these, anhydrous gypsum and semi-gypsum (mineral gypsum), which are inorganic dehydrating agents, are preferable. These dehydrating agents may be used singly or in combination of two or more kinds. On the other hand, the content of the dehydrating agent in the antifouling paint composition can be appropriately adjusted, and the total mass of the polyester resin (A), the silyl ester group-containing resin (B1) and the resin having a metal carboxylate structure It is preferably in the range of 0 to 100 mass%, more preferably in the range of 0.5 to 25 mass%.

The plasticizer is a component that contributes to improvement in crack resistance and water resistance of the obtained antifouling coating film. Examples of such plasticizers include tricresyl phosphate, dioctyl phthalate, chlorinated paraffin, liquid paraffin, n-paraffin, chlorinated paraffin, polybutene, terpene phenol, tricresyl phosphate (TCP), polyvinyl ethyl ether . These plasticizers may be used singly or in combination of two or more. On the other hand, when a plasticizer is added to the antifouling paint composition of the present invention, the content of the plasticizer in the antifouling paint composition is preferably such that the polyester resin (A), the silyl ester group-containing resin (B1) and the metal carboxylate structure Is preferably in the range of 0.5 to 10 mass%, more preferably in the range of 1 to 5 mass%, based on the total mass of the resin (B2).

Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol and the like.

Examples of the thixotropic agent include organic waxes (for example, polyethylene wax, polyethylene oxide wax, polyamide wax, amide wax, hydrogenated castor oil wax, etc.), organic clay based compounds (for example, Al, Ca, Zn Stearate salts, lecithin salts, alkylsulfonic acid salts and the like), bentonite, and synthesized fine silica. These thixotropic agents may be used singly or in combination of two or more kinds. When the thixotropic agent is compounded in the antifouling paint composition of the present invention, the content of the thixotropic agent in the antifouling paint composition can be appropriately adjusted. For example, the polyester resin (A) and the silyl ester group- ) And the resin (B2) having a metal carboxylate structure, based on the total mass of the resin (B2).

The antifouling paint composition of the present invention may contain one or more other kinds of resins (A), a silyl ester group-containing resin (B1) and a resin having a metal carboxylate structure It may contain tributaries. Examples of such resins include acrylic resins, acrylic silicone resins, epoxy resins, fluororesins, polybutene resins, silicone rubbers, urethane resins, polyamide resins, and vinyl chloride resins, which are widely used as gas resins for antifouling paints Styrene-butadiene copolymer resins, ketone resins, ethylene-vinyl acetate copolymer resins, vinyl chloride resins, alkyd resins, keratin resins, terpene phenol resins and petroleum resins.

The antifouling paint composition of the present invention may contain a known rosin compound. Examples of such rosin-based compounds include rosin, rosin derivatives, and rosin metal salts. Examples of the rosin include, for example, toluogene, chromogin, wood rosin and the like. Examples of the rosin derivatives include hydrogenated rosin, maleinized rosin reacted with rosin and maleic anhydride, formylated rosin, and polymerized rosin. Examples of the rosin metal salts include zinc rosinate, calcium rosinate, kapadoganate, magnesium rosinate, and a reaction product of a rosin with a metal compound. These rosin-based compounds may be used alone or in combination of two or more.

When the rosin-based compound is blended with the antifouling paint composition of the present invention, the content of the rosin-based compound in the antifouling paint composition is not particularly limited. For example, the content of the rosin- Is preferably 50 mass% or less, more preferably 30 mass% or less, based on the total mass of the resin (B1) and the resin (B2) having a metal carboxylate structure.

The anti-fouling coating composition of the present invention can be used in the form of a coating composition containing an aliphatic solvent, an aromatic solvent (e.g. xylene, toluene etc.), a ketone solvent (e.g., methyl isobutyl ketone, cyclohexanone, (For example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like), an alcohol solvent (for example, isopropyl alcohol), and the like, can do. On the other hand, the blending amount of the organic solvent can be appropriately adjusted. For example, the total solid content of the antifouling paint composition is in the range of 20 to 90% by mass, and may be further added depending on the workability at the time of coating.

The antifouling paint composition of the present invention can be prepared by the same method as the known antifouling paint composition. For example, the resin (A), the silyl ester group-containing resin (B1) and / or the resin (B2) having a metal carboxylate structure, the antifouling agent (C) Or the like in a stirring tank at one time or in succession, and stirring and mixing.

The coated article of the present invention is an article having a coated film of the antifouling coating composition of the present invention. The coated article may be obtained by a method including a step of coating or impregnating the surface of the substrate with the anti-fouling paint composition one to several times, and a step of drying the coated or impregnated anti-fouling paint composition have.

As the substrate, for example, a substrate which contacts (for example, always or intermittently) with seawater or fresh water, specifically, an underwater structure; Ship shell or bottom; Drain or cooling pipes of power plants; Fishing nets, fishing gears or floats used for these; Ropes, and the like. On the other hand, the film thickness of the coating film obtained from the antifouling coating composition of the present invention can be appropriately adjusted in consideration of the consumption rate (dissolution rate) of the coating film and the like. For example, the film thickness (mu m) / Time, preferably 75 to 150 占 퐉 / time, and may be set to about 60 to 500 占 퐉 by overlapping application twice as required.

In obtaining the coated article, the surface of the base material is coated with a primer, an antifouling paint and, if necessary, a binder paint, on the surface of the base material by means of brush coating, spray coating, roller coating, The antifouling paint composition may be applied. The antifouling coating composition of the present invention may be applied to the surface of the existing antifouling coating film in a superimposed manner. The coating film can be dried at room temperature, and may be heated and dried at a temperature up to about 100 캜, if necessary.

Example

Hereinafter, the present invention will be described more specifically by way of examples and comparative examples, but the present invention is not limited to the examples. In the following examples, "part" and "%" in the following examples mean "part by mass" and "mass%", respectively.

Production of polyester resin (A)

(Production Example 1) Production of polyester resin (A1)

415.3 parts of PA, 235.7 parts of NPG, 237.9 parts of DEG and 161.6 parts of lactide of lactic acid were put into a 2 L reactor equipped with a thermometer, a stirrer and a rectification column, and the content temperature of the reactor was raised to 160 캜 . Subsequently, the temperature of the contents of the reactor was raised from 160 ° C to 230 ° C over 3 hours, the content temperature was maintained at 230 ° C for 2 hours, the rectification column was replaced with a water separator, and about 50.0 parts The water and xylene were boiled together to remove condensation water, and polycondensation was carried out. After confirming that the acid value of the resulting polyester resin was 3.0 mgKOH / g or less, heating was stopped to start cooling, and xylene was added to dilute the solution to obtain a polyester resin (A1) solution having a solid content of 70%. On the other hand, the acid value of the above-mentioned resin was measured by dissolving the sample to be measured with a mixed solution of toluene and isopropanol (ratio by mass: 1/1) as a solvent, and titrating the alcohol-based solution of 1/10 of the specified potassium hydroxide .

Hereinafter, the relationship between the abbreviation of the polyester raw material in the present specification and the corresponding compound is shown below.

PA; Phthalic anhydride, iPA: isophthalic acid, AD; Adipic acid, HHPA; Hexahydrophthalic anhydride, EG; Ethylene glycol, PG; Propylene glycol, NPG; Neopentyl glycol, 1,6-HD; 1,6-hexanediol, BEPG; 2-butyl-2-ethyl-1,3-propanediol, CHDM; 1,4-cyclohexanedimethanol, DEG; Diethylene glycol, TEG; Triethylene glycol, tetra EG; Tetraethylene glycol, DPG; Dipropylene glycol, TMP; Trimethylol propane, G; Glycerin, PE; Pentaerythritol, LA; Lactide of lactic acid, GL; Glycolide

(Production Examples 2 to 8 and 13 to 17) Preparation of polyester resins (A2) to (A8), (A13) to (A17)

(A2) to (A8), (A13) to (A13), and (A13) to (A13) to (A13) to (A17) was obtained.

(Production Example 9) Production of polyester resin (A9)

340.9 parts of iPA, 215.6 parts of NPG, 217.7 parts of DEG and 147.8 parts of lactide of lactic acid were placed in a 2 L reaction apparatus equipped with a thermometer, a stirrer and a rectification column, and the content temperature of the reactor was raised to 160 캜 . Subsequently, the temperature of the contents of the reactor was raised from 160 ° C to 230 ° C over 3 hours, the content temperature was maintained at 230 ° C for 2 hours, the rectification column was replaced with a water separator, and about 45 parts of xylene The water and xylene were boiled together to remove condensation water, and polycondensation was carried out. After confirming that the acid value of the produced polyester resin was 3.0 mgKOH / g or less, the content temperature was cooled to 160 캜. Further, 152.0 parts of PA was added, and the addition reaction (half-esterification) was carried out at 160 DEG C for 1 hour to start cooling. After cooling to 130 캜, xylene was added and diluted to obtain a resin solution of a polyester resin (A9) having a solid content of 70%.

(Production Example 10) Production of polyester resin (A10)

292.8 parts of iPA, 185.2 parts of NPG, 186.9 parts of DEG and 127.0 parts of lactide of lactic acid were placed in a 2 L reaction apparatus equipped with a thermometer, a stirrer and a rectification column, and the content temperature of the reactor was raised to 160 캜 . Subsequently, the temperature of the contents of the reactor was raised from 160 ° C to 230 ° C over 3 hours, the content temperature was maintained at 230 ° C for 2 hours, the rectification column was replaced with a water separator, and about 45 parts of xylene The water and xylene were boiled together to remove condensation water, and polycondensation was carried out. After confirming that the acid value of the produced polyester resin was 3.0 mgKOH / g or less, the content temperature was cooled to 160 캜. Further, 276.1 parts of HHPA was added, and the mixture was subjected to addition reaction (half-esterification) at 160 DEG C for 1 hour, and then cooling was started. After cooling to 130 캜, xylene was added and diluted to obtain a resin solution of a polyester resin (A10) having a solid content of 70%.

(Production Example 11) Production of polyester resin (A11)

415.3 parts of PA, 235.7 parts of NPG, 237.9 parts of DEG, and 229.5 parts of 88% by mass of sulfuric acid aqueous solution were put into a 2 L reaction apparatus equipped with a thermometer, a stirrer and a rectification column, Lt; / RTI > Subsequently, the temperature of the contents of the reaction apparatus was raised from 130 ° C to 160 ° C over 3 hours, the content temperature was maintained at 230 ° C for 2 hours, the rectification column was replaced with a water separator, and about 50.0 parts The water and xylene were boiled together to remove condensation water, and polycondensation was carried out. After confirming that the produced polyester resin had an acid value of 3.0 mgKOH / g or less, heating was stopped to start cooling, and xylene was added to dilute to obtain a resin solution of a polyester resin (A11) having a solid content of 70%.

(Production Example 12) Production of polyester resin (A12)

217.4 parts of PA, 18.2 parts of EG, 205.7 parts of PE, 625.3 parts of soybean fatty acid, 28.2 parts of lactic acid of lactic acid and 50.0 parts of xylene were put into a 2 L reaction apparatus equipped with a thermometer, a stirrer and a rectification column, The temperature of the contents of the reactor was raised to 160 캜 and maintained for 1 hour. Then, the content temperature of the reaction apparatus was raised from 160 ° C to 240 ° C over 4 hours, and polycondensation proceeded while removing the condensed water generated at 240 ° C. After confirming that the resin acid value was about 3.0 mgKOH / g or less, heating was stopped to start cooling, and xylene was added to dilute to obtain a resin solution of a polyester resin (A12) having a solid content of 70%.

The resin acid value and the weight average molecular weight of the polyester resins (A1) to (A17) obtained in each of the above-mentioned Production Examples are shown in Table 1-1 together with the blending amounts of the respective production examples.

[Table 1-1]

(Production Example 1 ') Production of polyester resin (A1')

428.7 parts of PA, 243.3 parts of NPG, 245.7 parts of DEG and 134.4 parts of glycolide (GL) were charged into a 2 L reactor equipped with a thermometer, a stirrer and a rectification column, Respectively. Subsequently, the temperature of the contents of the reactor was raised from 160 ° C to 230 ° C over 3 hours, the contents were maintained at 230 ° C for 2 hours, the rectification column was replaced with a water separator, and about 50.0 parts The water and xylene were boiled together to remove condensation water, and polycondensation was carried out. After confirming that the produced polyester resin had an acid value of 3.0 mgKOH / g or less, heating was stopped to start cooling, and xylene was added to dilute to obtain a resin solution of a polyester resin (A1 ') having a solid content of 70%.

(Production Examples 2 'to 8', 13 'to 18') Production of polyester resins (A2 ') to (A'8), (A13') to (A18 ')

(A2 ') to (A8') having a solid content of 70% in the same manner as in Production Example 1 ', except that the acid component and the alcohol component in Production Example 1' (A13 ') to (A18').

(Production Example 9 ') Production of polyester resin (A9')

351.0 parts of iPA, 222.0 parts of NPG, 224.1 parts of DEG and 122.6 parts of glycolide were placed in a 2 L reaction apparatus equipped with a thermometer, a stirrer and a rectification column, and the content temperature of the reactor was raised to 160 캜. Subsequently, the temperature of the contents of the reactor was raised from 160 ° C to 230 ° C over 3 hours, the content temperature was maintained at 230 ° C for 2 hours, the rectification column was replaced with a water separator, and about 45 parts of xylene The water and xylene were boiled together to remove condensation water, and polycondensation was carried out. After confirming that the acid value of the produced polyester resin was 3.0 mgKOH / g or less, the content temperature was cooled to 160 캜. Further, 156.4 parts of PA was added, and the addition reaction (half-esterification) was carried out at 160 DEG C for 1 hour to start cooling. After cooling to 130 캜, xylene was added and diluted to obtain a resin solution of a polyester resin (A9 ') having a solid content of 70%.

(Production Example 10 ') Production of polyester resin (A10')

300.2 parts of iPA, 189.9 parts of NPG, 191.7 parts of DEG and 104.9 parts of glycolide were placed in a 2 L reaction apparatus equipped with a thermometer, a stirrer and a rectification column, and the content temperature of the reactor was raised to 160 캜. Subsequently, the temperature of the contents of the reactor was raised from 160 ° C to 230 ° C over 3 hours, the content temperature was maintained at 230 ° C for 2 hours, the rectification column was replaced with a water separator, and about 45 parts of xylene The water and xylene were boiled together to remove condensation water, and polycondensation was carried out. After confirming that the acid value of the produced polyester resin was 3.0 mgKOH / g or less, the content temperature was cooled to 160 캜. Furthermore, 278.5 parts of HHPA was added, and the mixture was subjected to addition reaction (half-esterification) at 160 DEG C for 1 hour, and then cooling was started. After cooling to 130 캜, xylene was added and diluted to obtain a resin solution of a polyester resin (A10 ') having a solid content of 70%.

(Production Example 11 ') Production of polyester resin (A11')

428.7 parts of PA, 243.3 parts of NPG, 245.7 parts of DEG and 176.1 parts of glycolic acid were put into a 2 L reaction apparatus equipped with a thermometer, a stirrer and a rectification column, and the content temperature of the reactor was raised to 130 캜. Subsequently, the temperature of the contents of the reaction apparatus was raised from 130 ° C to 160 ° C over 3 hours, the content temperature was maintained at 230 ° C for 2 hours, the rectification column was replaced with a water separator, and about 50.0 parts The water and xylene were boiled together to remove condensation water, and polycondensation was carried out. After confirming that the acid value of the resulting polyester resin was 3.0 mgKOH / g or less, the heating was stopped to start cooling, and xylene was added to dilute to obtain a resin solution of a polyester resin (A11 ') having a solid content of 70%.

(Production Example 12 ') Production of polyester resin (A12')

217.4 parts of PA, 18.2 parts of EG, 205.7 parts of PE, 625.3 parts of soybean oil fatty acid, 22.7 parts of glycolide and 50.0 parts of xylene were put into a 2L reaction apparatus equipped with a thermometer, a stirrer and a water separator, Was heated to 160 캜 and maintained at that temperature for 1 hour. Then, the content temperature of the reaction apparatus was raised from 160 ° C to 240 ° C over 4 hours, and polycondensation proceeded while removing the condensed water generated at 240 ° C. After confirming that the resin acid value was 3.0 mgKOH / g or less, heating was stopped to start cooling, and xylene was added and diluted to obtain a resin solution of a polyester resin (A12 ') having a solid content of 70%.

The resin acid value and the weight average molecular weight of the polyester resins (A1 ') to (A18') obtained in each of the above-mentioned Production Examples are shown in Table 1-2 together with the blending amounts of the respective production examples.

[Table 1-2]

Silyl ester group  Containing resin (B1)

(Production Example 18) Production of silyl ester group-containing resin (B1-1)

40 parts of xylene was placed in a flask equipped with a stirrer and the temperature of the liquid phase was maintained at 140 占 폚 and the unsaturated monomers shown in Table 2 and the peroxide-based polymerization initiator 'Perbutyl I' (trade name) 1 Was dropped into the flask for 3 hours, and after completion, kept at the same temperature for 30 minutes. Subsequently, a mixture of 10 parts of xylene and 1 part of 'Perbutyl I' (trade name) was dropped for 20 minutes and stirring was continued at the same temperature for 2 hours, followed by cooling of the liquid phase. Furthermore, xylene was added to the flask to prepare a solution of the resin so that the solid concentration became 50% by mass, to obtain a resin solution of the silyl ester group-containing resin (B1-1).

(Production Examples 19 and 20) Production of silyl ester group-containing resins (B1-2) and (B1-3)

A resin solution (solid concentration 50% by mass) of the silyl ester group-containing resins (B1-2) and (B1-3) was obtained in the same manner as in Production Example 18 except that the unsaturated monomer shown in Table 2 was used.

[Table 2]

metal Carboxylate  Preparation of Resin (B2) Having Structure

(Production Example 21) Production of resin (B2-1) having a metal carboxylate structure

241.7 parts of xylene, 197.5 parts of butyl acetate and 241.7 parts of n-butanol were put into a reaction vessel equipped with a thermometer, a thermometer, a stirrer, a reflux condenser and a dropping pump, and while stirring the contents in the reaction vessel, The temperature was raised to 105 ° C. Thereafter, a mixed solution containing 104.2 parts of methacrylic acid, 304.4 parts of ethyl acrylate, 272.4 parts of methoxyethyl acrylate, and 54.5 parts of 2,2-azobis (2-methylbutyronitrile) was heated to 105 ° C And dropped into the reaction vessel uniformly stirred over a period of 4 hours using a dropping pump at a constant rate. After completion of the dropping of the mixed solution, the temperature of the contents in the reaction vessel was maintained at 105 캜 for one hour, thereby obtaining an acrylic resin solution.

Further, the resin (B2-1) having a metal carboxylate structure with a non-volatile content of about 50% was obtained by adding 49.7 parts of zinc oxide and 34.0 parts of deionized water to the obtained resin solution and continuing stirring at 100 DEG C for 20 hours. Of a resin solution. The content of the metal atom contained in the resin (B2-1) (hereinafter simply referred to as the " metal content ") was 0.79 mol / Kg.

(Production Example 22) Production of resin (B2-2) having a metal carboxylate structure

563.0 parts of xylene and 140.7 parts of n-butanol were put into a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser and a dropping pump, and the temperature of the mixed solution in the reaction vessel was maintained at 110 DEG C to 120 DEG C. A mixed solution containing 281.5 parts of ethyl acrylate, 117.3 parts of 2-ethylhexyl acrylate, 70.4 parts of acrylic acid and 37.5 parts of 2,2-azobis (2-methylbutyronitrile) was added to the solution at a constant rate for 3 hours Lt; / RTI > After completion of the dropping of the mixed solution, the temperature of the mixed solution was maintained at 110 캜 to 120 캜 for 2 hours to obtain an acrylic resin solution.

Further, 236.4 parts of naphthenic acid and 82.8 parts of copper hydroxide were added to the obtained resin solution, and the temperature was raised to 120 占 폚 and held for 2 hours. The resulting water was removed (about 30 parts of dehydration yield) to obtain a resin solution of a resin (B2-2) having a metal carboxylate structure with a non-volatile content of about 50%. The metal content of this resin (B2-2) was 1.08 mol / Kg.

On the other hand, the content of metal such as zinc and copper in the resin was quantified by fluorescent X-ray method.

[Table 3]

Preparation and various tests of antifouling paint compositions

(Examples 1 to 28) and (Comparative Examples 1 to 8) and (Examples 29 to 57) and (Comparative Examples 9 to 16)

evaluation

The resin solutions of the polyester resins (A1) to (A17) and (A1 ') to (A18'), the silyl ester group-containing resins (B1-1) to (B1-3), the resins having the metal carboxylate structure The resin solution of B2-1) and (B2-2), antifouling agent, pigment and the like were compounded in the blending composition shown in Tables 4-1 to 4-4, and mixed and dispersed using a homomixer at a stirring speed of about 2000 rpm Respectively. After dispersing, Diparron A630-20XN (a flow inhibitor, manufactured by Cuslimokase Co., Ltd.) and a solvent were added and dispersed with stirring to prepare coating compositions (E1) to (E73). The coating composition thus prepared was evaluated for the antifouling performance test (the test results are shown in Tables 5-1 to 5-4), the adhesion test (the test results are shown in Tables 6-1 to 6-4) and the crack resistance test And the test results are shown in Tables 7-1 to 7-4).

<Antifouling performance test>

Spray coating was performed on both sides of a sandblast treated steel sheet (100 mm x 300 mm x 2 mm) so as to obtain a dry film thickness of 200 m and an epoxy-based binder coat was further coated to a dry film thickness of 100 m . Each coating composition was coated on both sides of the coating plate by spray coating so as to have a dry film thickness of 480 μm on one side and dried for 1 week in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75% Respectively. Using this test piece, 60-month seawater soaking was carried out by Mie Ken and Saja Laura, Minami-Ise-machi, Taro-gun, and the ratio of the occupied area of the adhering creature on the test coat film (adhesion area) was measured with time.

◎: (Passed) No attached organisms were observed

○: (Passed) Occupied area of attached organisms is less than 5%

△: (Failed) Occupied area of attached organisms is over 5%, less than 30%

X: (Failed) 30% or more occupied area of attached organisms

<Adhesion Test>

(120 mm x 120 mm x 1 mm) having a softness capable of being mounted on a cylindrical drum (500 mm in diameter x 240 mm in height) was spray-coated with an epoxy-based rust preventive paint so as to have a dry film thickness of 200 m, The epoxy-based binder coat was coated so as to have a dry film thickness of 100 mu m. Each coating composition was painted four times by spray coating so as to have a dry film thickness of 480 탆 on one side of the coated steel sheet and dried for one week in a constant temperature and humidity chamber at a temperature of 20 캜 and a humidity of 75% . These test pieces were mounted on the above-mentioned cylindrical drum, and the cylindrical drum was rotated for 24 months at 16 knots at 500 mm under the sea surface of Hyogo Ken Yura Bay. The test pieces were recovered in the seawater over time to form a 5 mm x 5 mm grid, and the adhesion of the test pieces was evaluated by tape peeling. The evaluation was made in accordance with ISO 2409: 1992.

◎: (Pass) Table1 Classification 0 · 1

○: (Passed) Table1 Classification 2

△: (Failed) Table1 Classification 3

×: (Failed) Table1 Classification 4 · 5

&Lt; Crack resistance test >

The coating film of the test piece provided in the adhesion test was visually observed to examine the occurrence of cracks.

◎: (Passed) No crack was observed

○: (Pass) A slight crack was observed on the surface of the coating film.

△: (Failure) Although not reaching the bottom, fine and clear cracks were observed on the surface of the film.

×: (Failure) Cracks reaching the floor were observed.

[Table 4-1]

[Table 4-2]

[Table 4-3]

[Table 4-4]

[Table 5-1] Pollution prevention performance test

[Table 5-2] Pollution prevention performance test

[Table 5-3] Pollution prevention performance test

[Table 5-4] Pollution prevention performance test

[Table 6-1] Adhesion test

[Table 6-2] Adhesion test

[Table 6-3] Adhesion test

[Table 6-4] Adhesion test

[Table 7-1] Crack resistance test

[Table 7-2] Crack resistance test

[Table 7-3] Crack resistance test

[Table 7-4] Crack resistance test

Claims (7)

An antifouling coating composition comprising a polyester resin (A), a silyl ester group-containing resin (B1) and / or a resin (B2) having a metal carboxylate structure, and a antifouling agent (C)
Wherein the polyester resin (A) has a constitutional unit represented by the following formula (1) in its resin skeleton, and the total mass of the constitutional unit represented by the following formula (1) is, based on the mass of the polyester resin (A) By mass to 2% by mass to 50% by mass,
Characterized in that the mass ratio of the polyester resin (A) to the total of the silyl ester group-containing resin (B1) and the resin (B2) having the metal carboxylate structure is in the range of 3/97 to 80/20 Based on the total weight of the coating composition.
[Chemical Formula 1]

(Wherein R ₀ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 100) The method according to claim 1,
Wherein the silyl ester group-containing resin (B1) is one or two or more kinds of monomers (b1) represented by the following formula (2) and one or more kinds of monomers (b2) other than the monomer (b1) By weight based on the total weight of the coating composition.
(2)

[Wherein, R ₄ represents a hydrogen atom or a methyl group, R _1, R ₂ and R ₃ each independently represent a hydrocarbon group, R ₅ is a hydrogen atom or R ₆ -O-CO- (However, R ₆ metaphor Or a silyl group represented by -SiR ₇ R ₈ R ₉ , and R ₇ , R ₈ and R ₉ each independently represent a hydrocarbon group. 3. The method according to claim 1 or 2,
Wherein the resin (B2) having the metal carboxylate structure has a characteristic group having a metal carboxylate structure represented by the following formula (3), wherein the metal atom (s) contained in the resin (B2) having the metal carboxylate structure Is in the range of 0.04 to 3.50 mol / Kg based on the solid content of the resin (B2).
(3)

(Wherein M represents a divalent metal atom and X represents at least one group selected from the group consisting of a hydroxyl group, an organic acid residue and an alcohol residue). 4. The method according to any one of claims 1 to 3,
Wherein the polyester resin (A) is selected from the group consisting of lactic acid, a raw material mixture containing at least one component selected from the group consisting of lactide and lactic acid lactic acid, and glycolic acid, glycolide and polyglycolic acid , And the acid value of the polyester resin (A) is in the range of 0.1 to 120 KOH mg / g. The polyester resin (A) is a polyester resin prepared by using at least one raw material mixture of a raw material mixture containing at least one kind of component Antifouling paint composition. 5. The method according to any one of claims 1 to 4,
Wherein the polyester resin (A) has a weight average molecular weight in the range of 190 to 15,000. 6. The method according to any one of claims 1 to 5,
Wherein the polyester resin (A) does not have a metal carboxylate structure. A painted article having a coating film of the antifouling paint composition according to any one of claims 1 to 6.