TW201542725A - Antifouling coating material composition and coated article coated with same - Google Patents

Abstract

The purpose of the present invention is to provide: an antifouling coating material composition which is capable of forming an antifouling coating film that is able to maintain excellent antifouling properties for a long period of time and is not susceptible to the occurrence of coating film defects such as coating film separation, blisters and cracks; and a coated article which is obtained by coating an object to be coated such as a fishing net, a boat or ship, or a structure in the ocean or on the gulf coast with the antifouling coating material composition. The present invention provides: an antifouling coating material composition which contains (A) a specific polyester resin, (B) a silyl ester group-containing resin and (C) an antifouling agent; and a coated article which is coated with the composition.

Description

Antifouling coating composition, and coated article formed by coating the composition

The present invention relates to an antifouling coating composition, and a coated article comprising the composition, and more particularly to an antifouling coating which can form an antifouling coating film which can maintain excellent antifouling properties for a long period of time. a composition, and a coated article comprising the composition coated on the object to be coated.

In recent years, as a resin for an antifouling coating containing a tin-based copolymer which is a concern for marine pollution, various resins have been examined for introducing an antifouling coating resin which can be ester-bonded in seawater to a polymer side chain. Wherein, the antifouling coating composition containing a trialkyl decyl ester-based resin is hydrolyzed in seawater because the trialkyl decyl ester moiety is hydrolyzed, so that the coating film obtained from the antifouling coating composition described above has a slow dissolution from the surface to the seawater. The nature of this is finally put to practical use as a resin for antifouling coatings.

The dissolution rate of such a coating film containing a trialkyl decyl ester-based resin varies depending on the structure of the trialkyl decyl ester group. For example, the antifouling coating composition containing a tri-n-butyl decyl ester-based resin is difficult to maintain the antifouling property of the coating film for a long period of time because the dissolution rate of the obtained coating film is fast. On the other hand, the antifouling of the triorganomethane ester-based resin having a branched alkyl group bonded to a ruthenium atom is used. Since the coating composition has a slow dissolution rate of the obtained coating film, there is a problem in that it is easy to adhere to aquatic organisms in a sea area where sea water temperature is low. Therefore, regarding the antifouling coating composition of the latter, a method of controlling the dissolution rate of the coating film by adding rosin or a rosin derivative has been examined (Patent Documents 1 to 3). However, in this method, when the amount of use of the rosin or the rosin derivative is small, the solubility of the coating film in seawater is not sufficiently obtained, and the antifouling effect is not easily maintained. On the other hand, when the amount of use of the rosin or the turpentine derivative is large, the dissolution rate of the coating film is increased, and the antifouling effect is improved, but the physical properties or adhesion of the coating film are lowered, and the long-term maintenance of the antifouling effect is difficult. There is a tendency that coating film defects such as peeling of the coating film, blister, and cracking are likely to occur.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 10-30071

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-53797

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-26357

An object of the present invention is to provide an antifouling coating composition which can maintain excellent antifouling properties over a long period of time and which can form an antifouling coating film which is less likely to cause coating film peeling, blistering, cracking or the like, and provide an antifouling coating composition. The antifouling coating composition is applied to a coated article such as a fishing net, a ship, a structure such as a sea or a bay shore, or the like.

The present inventors have conducted an active review to achieve the above object, and found that the coating film obtained by using a specific polyester resin and an antifouling coating composition containing a decyl ester-based resin can control the dissolution rate of the coating film in the ocean. Moreover, it is excellent in the physical properties of the coating film which can maintain excellent antifouling properties for a long period of time. Therefore, when the antifouling coating composition is applied to the bottom of a ship, it is difficult to cause peeling, blistering, cracking of the coating film during navigation or mooring. Such as film defects. The present invention has been completed based on this finding.

The present invention provides the following antifouling coating composition and a coated article obtained by applying the antifouling coating composition to an object to be coated.

Item 1. An antifouling coating composition comprising an antifouling coating composition comprising a polyester resin (A), a decyl ester-based resin (B), and an antifouling agent (C), characterized by the aforementioned decyl ester-containing ester The base resin (B) is derived from the general formula (I): R ⁵ -CH=C(R ⁴ )-COO-SiR ¹ R ² R ³ . . . (I)

[In the formula (I), 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 represents a hydrogen atom or R ⁶ -O-CO- (However, R ⁶ represents an organic Or the alkyl group represented by -SiR ⁷ R ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ⁹ each independently represent one or more of the monomers (b1) represented by the hydrocarbon group), and the above monomers a copolymer of one or more monomers (b2) other than (b1), wherein the mass ratio of the polyester resin (A) to the decyl ester-containing resin (B) is 3/97 to 80/ In the range of 20, the content of the antifouling agent (C) is in the range of 50 to 500% by mass based on the total mass of the polyester resin (A) and the decyl ester-containing resin (B).

The antifouling coating composition according to the item 1, wherein the polyester resin (A) has an acid value in the range of 0 to 120 KOHmg/g.

The antifouling coating composition according to the first or second aspect, wherein the polyester resin (A) has a weight average molecular weight of 15,000 or less.

The antifouling coating composition according to any one of the items 1 to 3, wherein the mass ratio of the polyester resin (A) to the decyl ester-containing resin (B) is 7/93. Within the range of 60/40.

The antifouling coating composition according to any one of the items 1 to 4, wherein the decyl ester-containing resin (B) is a mass of the monomer (b1) and the monomer (b2). The ratio (b1)/(b2) is in the range of 20/80 to 70/30.

Item 6. A coated article, which is characterized in that the article to be coated is coated with the antifouling paint composition according to any one of items 1 to 5.

The antifouling coating composition of the present invention can form a coating film which can maintain excellent antifouling properties for a long period of time and which is less likely to cause coating film defects such as peeling of the coating film, foaming, and cracking.

The antifouling coating composition of the present invention comprises an antifouling coating composition comprising a polyester resin (A), a decyl ester-based resin (B) and an antifouling agent (C), characterized by the aforementioned decyl ester-containing resin (B) ) is derived from the general formula (I): R ⁵ -CH=C(R ⁴ )-COO-SiR ¹ R ² R ³ . . . (I)

[In the formula (I), 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- (only, R ⁶ represents an organic group). Or the alkyl group represented by -SiR ⁷ R ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ⁹ each independently represent one or more of the monomers (b1) represented by the hydrocarbon group), and the above monomers a copolymer of one or more monomers (b2) other than (b1), wherein the mass ratio of the polyester resin (A) to the decyl ester-containing resin (B) is 3/97 to 80/ In the range of 20, the content of the antifouling agent (C) is in the range of 50 to 500% by mass based on the total mass of the polyester resin (A) and the decyl ester-containing resin (B). Hereinafter, the antifouling coating composition of the present invention will be described in detail.

[Polyester Resin (A)]

The polyester resin (A) used in the antifouling coating composition of the present invention can have the acid component (a1) and the alcohol component (a2) as main raw materials, and the esterification reaction and/or transesterification reaction of the components. Manufacturing.

Acid component (a1)

In the present invention, as the acid component (a1), an acid component which is usually used in the production of a polyester resin can be used. The acid component is exemplified by, for example, an alicyclic polybasic acid or a lipid. Aliphatic polybasic acids, aromatic polybasic acids, aromatic monocarboxylic acids, aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and esters, anhydrides and halides of such acids.

As the alicyclic polybasic acid, a compound having one or more alicyclic structures (mainly 4 to 6 membered rings) and two or more carboxyl groups in one molecule, and an acid anhydride, an esterified product and a halide of the compound can be used. Such an alicyclic polybasic acid is exemplified by, for example, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-cyclohexene-1. ,2-dicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-carboxylic acid, tetrahydromethylphthalic acid, 3-methyl-1 , 2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid An alicyclic polyvalent carboxylic acid such as an acid; an acid anhydride of the alicyclic polycarboxylic acid; a lower alkyl esterified product of the alicyclic polycarboxylic acid; and the like. These may be used alone or in combination of two or more.

As the aliphatic polybasic acid, an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, a halide of the aliphatic compound, or the like can be used. Such aliphatic polybasic acids are exemplified by, for example, succinic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, eleven An aliphatic polycarboxylic acid such as alkanoic acid, dodecanedioic acid, brasylic acid, octadecanedioic acid or citric acid; an anhydride of the aliphatic polycarboxylic acid; and said aliphatic polycarboxylic acid These may be used singly or in combination of two or more kinds.

Aromatic polybasic acids can generally be used in 2 molecules. An aromatic compound of the above carboxyl group, an acid anhydride of the aromatic compound, an esterified product of the aromatic compound, and a halide of an aromatic compound.

The aromatic polybasic acid having two carboxyl groups in one molecule is exemplified by aromatic polycarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid or 4,4'-biphenyldicarboxylic acid. An acid; an acid anhydride of the aromatic polycarboxylic acid, and the like.

The aromatic polybasic acid having three or more carboxyl groups in one molecule is exemplified by, for example, a three-membered aromatic polycarboxylic acid and a four-membered aromatic polycarboxylic acid. The trivalent aromatic polycarboxylic acid is exemplified by trimellitic acid such as trimellitic acid, trimellitic anhydride, alkyl trimellitate, trimellitic acid halide, etc.; hemirimic acid, trimellitic anhydride a pyromellitic acid such as a trimellitic acid alkyl ester or a pyromellitic acid halide; a trimesic acid such as trimesic acid, an alkyl trimellitate or a trimesic acid halide; Various naphthalene tricarboxylic acids and their anhydrides having different bonding positions to the aromatic ring; various hydrazine tricarboxylic acids and their anhydrides having different bonding positions of carboxyl groups to aromatic rings; various biphenyls having different bonding positions of carboxyl groups to aromatic rings a tricarboxylic acid and an acid anhydride thereof; various benzophenone tricarboxylic acids and an acid anhydride thereof having different bonding positions of a carboxyl group to an aromatic ring; and an ethyl ditrim trimomic acid and an acid anhydride thereof. Further, the 4-membered aromatic polycarboxylic acid is exemplified by pyromellitic acid such as pyromellitic acid, pyromellitic dianhydride, alkyl pyromellitate, and pyromellitic acid halide; , benzoic acid dianhydride, benzene tetracarboxylic acid alkyl ester, benzotetracarboxylic acid halide and other benzotetracarboxylic acid; benzene tetracarboxylic acid (prehnitic acid), pyromellitic anhydride, alkyl benzene tetracarboxylate, pyromellitic acid A benzenetetracarboxylic acid such as a halide. The above aromatic polybasic acids may be used singly or in combination of two Used above.

In the present invention, a monocarboxylic acid such as an aromatic monocarboxylic acid, an aliphatic monocarboxylic acid or an alicyclic monocarboxylic acid may be used as the acid component (a1) used for the production of the polyester resin (A). The aromatic monocarboxylic acid is exemplified by, for example, benzoic acid, methylbenzoic acid, ethylbenzoic acid, p-t-butylbenzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzene. Formic acid, phenoxyacetic acid, biphenyl carboxylic acid, and the like. Further, the aliphatic monocarboxylic acid is exemplified by, for example, acetic acid, lactic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, caprylic acid, citric acid, citric acid, undecanoic acid, Lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, elaidic acid, brassic acid, linoleic acid, linolenic acid, rosin acid, coconut fatty acid, cottonseed oil fatty acid Hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tallow fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, sunflower oil fatty acid, etc. The saturated aliphatic monocarboxylic acid may be used singly or in combination of two or more.

The above alicyclic monocarboxylic acid is exemplified by, for example, cyclohexanecarboxylic acid, cyclopentanecarboxylic acid, cycloheptanecarboxylic acid, 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-lauric acid These may be used singly or in combination of two or more kinds.

In the present invention, the acid component (a1) used in the production of the polyester resin (A) also contains an esterified product such as a glyceride of the above monocarboxylic acid. The glycerides of monocarboxylic acids are exemplified by, for example, coconut oil, cottonseed oil, hemp seed oil, rice bran oil, fish oil, tallow, soybean oil, linseed oil, tung oil, rapeseed oil, castor oil, Dehydrated castor oil, sunflower oil, etc.

Further, in the present invention, the acid component (a1) used for the production of the polyester resin (A) preferably contains an aromatic polybasic acid based on the long-term maintenance of the antifouling property, and the content thereof is a total of the acid components (a1). The number is 30 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more.

Alcohol content (a2)

In the present invention, as the alcohol component (a2), an alcohol component which is usually used in the production of a polyester resin can be used. The alcohol component is preferably a dihydric alcohol such as an alicyclic diol, an aliphatic diol or an aromatic diol, and/or a trihydric or higher polyhydric alcohol, and is exemplified by, for example, ethylene glycol, diethylene glycol, and trisole. Ethylene glycol, tetraethylene glycol, pentaethylene glycol, 1,2-propanediol, di-1,2-propanediol, tri-1,2-propanediol, 1,2-butanediol, 2,3-butane Alcohol, 1,2-hexanediol, 1,2-dihydroxycyclohexane, 3-ethoxypropane-1,2-diol, 3-phenoxypropane-1,2-diol, neopentyl Glycol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexyl Glycol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propanediol , 2-phenoxypropane-1,3-diol, 2-methyl-2-phenylpropane-1,3-diol, 1,3-propanediol, 1,3-butanediol, 2-B -1,3-octanediol, 1,3-dihydroxycyclohexane, 1,4-butanediol, 1,4-dihydroxycyclohexane, 1,5-pentanediol, 1,6- Hexanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,4-dimethylolcyclohexane, tricyclodecane dimethanol, 2,2-dimethyl 3-hydroxypropane-2,2-dimethyl-3-hydroxypropionate Esterification of valeric acid with neodiol , bisphenol A, bisphenol F, alkylene oxide adduct of bisphenol A, bis(4-hydroxyhexyl)-2,2-propane, bis(4-hydroxyhexyl)methane, 3,9-double (1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, bis(hydroxyethyl)terephthalate, etc. Ester diol compound, diethylene glycol, triethylene glycol, glycerin, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, mannitol, trishydroxyl Methyl ethane, trimethylolpropane, di-trimethylolpropane, ginseng (2-hydroxyethyl)isocyanurate, and addition of lactone compounds such as ε-caprolactone to the polyols The polylactone polyol compound or the like may be used alone or in combination of two or more.

In addition, methanol, ethanol, propanol, n-butanol, isobutanol, second butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, nonanol, cyclohexanol, Monools such as benzyl alcohol, stearyl alcohol, 2-phenoxyethanol, and dodecyl alcohol; glycidyl esters of ethylene oxide, propylene oxide, butylene oxide, and synthetic high-branched fatty acids (trade name "CARDURA" An alcohol compound obtained by reacting a monoepoxy compound such as E10"HEXION Specialty Chemicals Co., Ltd. with a compound having a protonic acid; a metal-containing alcohol compound such as zinc lactate or the like as an auxiliary material in the production of the polyester resin (A).

In the present invention, the method for producing the polyester resin (A) is not particularly limited, and a usual method can be employed. The polyester resin (A) can be reacted at a temperature of 150 to 250 ° C by, for example, one or two or more kinds of the acid component (a1) and one or more alcohol components (a2) in a nitrogen stream. It is produced by an esterification reaction and/or a transesterification reaction for 2 to 10 hours. Esterification In the reaction and/or transesterification reaction, the acid component (a1) and the alcohol component (a2) may be added at once, or may be added in portions. The above reaction can also be carried out in the presence of a conventional organic solvent.

Further, the polyester resin (A) may be obtained by first synthesizing a carboxyl group-containing polyester resin and then esterifying one of the carboxyl groups of the carboxyl group-containing polyester resin using the above alcohol component (a2). Further, the polyester resin (A) may be obtained by first synthesizing a hydroxyl group-containing polyester resin and then reacting the hydroxyl group-containing polyester resin with the above acid anhydride.

Further, a catalyst may be used to promote the reaction in the above esterification reaction and/or transesterification reaction. Such catalysts are exemplified by, for example, dibutyltin oxide, antimony trioxide, iron acetate, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, tetraisopropyl titanate, zinc borate, chlorine. Known catalysts such as zinc, zinc sulfate, zinc naphthenate, lead borate, lead acetate, manganese acetate, aluminum acetate, and aluminum chloride.

In the present invention, the polyester resin (A) is produced by using an acid component (a1) and an alcohol component (a2) as main raw materials, and is produced by an esterification reaction and/or a transesterification reaction of the respective components, but may be optionally used. A conventional organic and/or inorganic compound other than the constituent components derived from the acid component (a1) and the alcohol component (a2) is contained as a constituent component, accompanied by a guanidation reaction, a urethanization reaction, and a hydrazine reaction. It is produced by a conventional chemical reaction such as an imidization reaction, a carboxylic acid esterification reaction, or a urea conversion reaction. For example, the polyester resin (A) may be in the reaction of the esterification reaction and/or the transesterification reaction or after the reaction, by reacting the reaction intermediate or the reaction product with the organic acid zinc, the organic acid copper, the zinc chloride, Copper chloride, zinc hydroxide, copper hydroxide, zinc oxide, oxygen Modified polyester resin obtained by reacting a metal compound such as copper, a fatty acid, a fat or oil, a mono- or polyisocyanate compound, a mono- or polyamine compound having a nitrogen atom bonded to a hydrogen atom, an epoxy compound, an acrylic resin, a vinyl ester resin, or the like .

The constituent component of the polyester resin (A) derived from the acid component (a1) and the alcohol component (a2) is preferably 80 mol% or more, more preferably 90 mol% or more of all the constituent components of the resin.

Further, the resin acid value of the polyester resin (A) is preferably in the range of 0 to 120 mgKOH/g, more preferably 0 to 95 mgKOH/g, from the viewpoint of maintaining the antifouling property of the obtained coating film for a long period of time. It is preferably in the range of 0 to 45 mgKOH/g.

Further, the weight average molecular weight of the polyester resin (A) is preferably from 15,000 or less, more preferably from 190 to 7,000, in terms of the antifouling property of the obtained coating film and the antifouling property in a long period of time. It is in the range of 500~4,000.

The weight average molecular weight in the present specification is a value converted from a weight average molecular weight measured by a gel permeation chromatography ("HLC8120GPC" manufactured by TOSOH Co., Ltd.) based on the weight average molecular weight of polystyrene. For the measurement of the weight average molecular weight, four columns (trade name "TSKgel G-4000H×L", "TSKgel G-3000H×L", "TSKgel G-2500H×L", and "TSKgel G-2000H×L" can be used. All are made of TOSOH (manufactured by the company), and the mobile phase: tetrahydrofuran, measuring temperature: 40 ° C, flow rate: 1 ml / minute, detector: RI conditions.

[Hydrogen-containing resin (B)]

The antifouling coating composition of the present invention further contains a decyl ester-containing resin (B) in addition to the above polyester resin (A). The decyl ester-containing resin (B) is a monomer (b1) having a polymerizable unsaturated group and a triorganomenyl ester group represented by the following general formula (I) (hereinafter, sometimes referred to as "monomer (b1)" One or two or more kinds of copolymers of one or two or more kinds of monomers (b2) having a polymerizable unsaturated group other than the above monomer (b1), and preferably having a weight average molecular weight (Mw) is in the range of 1,000 to 150,000, and the weight average molecular weight (Mw) is in the range of 3,000 to 80,000.

R ⁵ -CH=C(R ⁴ )-COO-SiR ¹ R ² R ³ . . . (I)

[In the formula (I), 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- (only, R ⁶ represents an organic group). Or a decyl 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 decyl ester-containing resin (B) used in the antifouling coating composition of the present invention is less than 1,000, the coating speed of the coating film obtained from the antifouling coating composition is large, but the coating property is poor and easy. Foaming or cracking. When the Mw of the decyl ester-containing resin (B) exceeds 150,000, the dissolution rate of the coating film obtained from the antifouling coating composition may be slow, and the antifouling property may be inferior.

When R ⁵ in the above formula (I) of the monomer (b1) is a hydrogen atom, it is represented by the following formula (I-1): CH ₂ = C(R ⁴ )-COO-SiR ¹ R ² R ³ . . . . . (I-1)

^4, R ^1, R ² and R ^{3 are} the same as in general formula (I-1) in the R ^4, R ^1, R ² and R ³ in the above formula (I), the R.

The hydrocarbon group in R ¹ , R ² and R ³ in the above formula (I) or the above formula (I-1) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or may be optionally substituted A phenyl group which is substituted or unsubstituted, and each hydrocarbon group may be the same or different. Among them, an alkyl group having 1 to 5 carbon atoms is preferred, and an alkyl group such as methyl, ethyl, propyl, n-butyl, t-butyl, t-butyl or isopropyl is preferred.

The monomer represented by the above formula (I-1) (hereinafter referred to as "monomer (b1-1)") is exemplified by, for example, trimethyl decyl (meth) acrylate or triethyl decyl (meth) acrylate. And a trialkyl decyl (meth) acrylate such as triisopropyl decyl (meth) acrylate, wherein the solubility of the obtained coating film, the durability of the antifouling property, and the occurrence of blistering or cracking are less likely to occur. From the viewpoint of the like, triisopropyl methacrylate (meth)acrylate is preferred.

The monomer (b1) is that R ⁵ in the above formula (I) is "R ⁶ -O-CO-" (except that R ⁶ represents an organic group or a decyl group represented by -SiR ⁷ R ⁸ R ⁹ , R ⁷ when, R ⁸ and R ⁹ each independently represents a hydrocarbon group), the following formula is represented by an (I-2).

R ⁶ -O-CO-CH=C(R ⁴ )-COO-SiR ¹ R ² R ³ . . . . (I-2)

Further, the formula R (I-2) in the ^4, R ^1, R ² and R ^{3 are} the same, respectively, in the above formula (I) or the formula (I-1) in the R ^4, R ^1, R ² and R ³ .

The organic group in R ⁶ in the above formula (I), the above formula (I-1) or the above formula (I-2) is exemplified by a linear or branched alkyl group or a naphthene having a carbon number of 1 to 10. Base, unsaturated alkyl, aralkyl, and the like.

The above linear or branched alkyl group having 1 to 10 carbon atoms is exemplified by, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an isobutyl group, a n-butyl group, a second butyl group, and a third butyl group. Base, 2-methylbutyl, 2-ethylbutyl, pentyl, 3-methylpentyl, hexyl, heptyl, octyl and the like.

Further, the above cycloalkyl group is exemplified by, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like.

The above unsaturated alkyl group is exemplified by 2-propenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl and the like.

The above aralkyl group is exemplified by a benzyl group, a phenethyl group, a phenylpropyl group or the like.

Further, the alkyl group, the cycloalkyl group, the unsaturated alkyl group and the aralkyl group may have a substituent. Such a substituent is exemplified by, for example, an alkoxy group, a decyl group or the like. Further, the number of substituents, the position of substitution, and the like are not particularly limited as long as they do not impair the effects of the present invention.

The monomer represented by the above formula (I-2) (hereinafter referred to as "monomer (b1-2)") is exemplified by, for example, a maleic acid diester compound and a fumaric acid diester compound (in the formula (I-2)). R ⁴ is a hydrogen atom) and the like.

The formula (I), the formula (I-1) or the formula (I-2) of the R ^7, R ⁸ and R ⁹ is preferably a hydrocarbon group of carbon number 1 ~ 10 linear or branched chain having the The alkyl group or the phenyl group substituted or unsubstituted with any substituent may be the same or different. Among them, an alkyl group having 1 to 5 carbon atoms is preferred, and an alkyl group such as methyl, ethyl, propyl, n-butyl, t-butyl, t-butyl or isopropyl is preferred.

The monomer (b1) is preferably an isopropylidene group-containing unsaturated monomer from the viewpoints of solubility of the coating film, durability of the antifouling property, and difficulty in occurrence of foaming or cracking. Such isopropyl decyl-containing unsaturated monomers are exemplified by, for example, triisopropyldecyl (meth)acrylate, triisopropyldecyl 4-pentenoate, bis(triisopropyldecane) maleate. Ester, methyl triisopropyl decyl maleate, ethyl triisopropyl decyl maleate, n-butyl triisopropyl decyl maleate, isobutyl triisopropyl maleate Pyridyl ester, tert-butyltriisopropyldecyl maleate, n-pentyltriisopropyldecyl maleate, isoamyltriisopropyldecyl maleate, 2-ethyl maleate Trihexyl triisopropyl decyl ester, cyclohexyl triisopropyl decyl maleate, bis(triisopropyldecyl) fumarate, methyl triisopropyl decyl fumarate, fumaric acid Ethyl triisopropyl decyl ester, n-butyl triisopropyl decyl fumarate, isobutyl triisopropyl decyl fumarate, n-pentyl triisopropyl decyl fumarate, Fu Ma Acid isoamyl triisopropyl decyl ester, 2-ethylhexyl triisopropyl decyl fumarate, cyclohexyl triisopropyl decyl fumarate, etc., especially triisopropyl (meth) acrylate A decyl ester is preferred. Further, these triisopropyldecyl group-containing monomers may be used singly or in combination of two or more.

The decyl ester-containing resin (B) is preferably obtained by copolymerizing the monomer (b1) and the monomer (b2) in a mass ratio (b1)/(b2) in the range of 20/80 to 70/30, more preferably It is preferred that the monomer (b1) and the monomer (b2) are copolymerized in a mass ratio (b1)/(b2) in the range of 30/70 to 60/40.

When the mass ratio (b1)/(b2) is less than 20/80, it will be When the dissolution rate of the coating film is slow and the antifouling performance is poor, when the mass ratio (b1)/(b2) is more than 70/30, the solubility of the obtained coating film becomes large, but it is difficult to maintain the antifouling effect for a long time. The situation.

The monomer (b2) copolymerizable with the monomer (b1) (or the monomer (b1-1) and/or (b1-2)) may be exemplified by methyl (meth)acrylate or (meth)acrylic acid Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc. (meth)acrylic acid alkyl esters; 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, (A) (meth)acrylic acid alkoxyalkyl esters such as 2-ethoxyethyl acrylate; (meth)acrylic acid monomethyl ester, single molecule terminal alkoxy group and polyoxyethylene ethyl chain (meth) acrylate, a single molecular end alkoxy group and a polyoxyalkylene propyl (meth) acrylate, (meth) propylene glycol monomethyl methacrylate (meth) acrylate Methyl esters; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid and carbon 2 to 8 The ε-caprolactone modified monoester of the alcohol, the allyl alcohol, and the molecular end is hydroxyl And a hydroxyalkyl (meth) acrylate having a hydroxyl group-containing monomer such as a polyoxyethylene chain (meth) acrylate; (meth)acrylonitrile, (meth) acrylamide, N, N-Dimethyl(meth)acrylamide, (meth)propenylmorpholine, N-isopropyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N - alkoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylate Aminoethyl ester, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth) acrylamide, glycidyl (meth)acrylate a nitrogen-containing monomer such as an amine-added product; (meth) acrylate such as benzyl (meth) acrylate or phenyl (meth) acrylate; vinyl chloride; vinylidene chloride; (meth) propylene Nitrile; vinyl acetate; butyl vinyl ether; lauryl vinyl ether; N-vinyl pyrrolidone; styrene; vinyl toluene; Further, as the monomer (b2), for example, a vinyl ester compound such as vinyl propionate or vinyl acetate; (meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, a carboxyl group-containing monomer such as crotonic acid or β-carboxyethyl (meth)acrylate; glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and (meth)acrylic acid 3,4 - Epoxycyclohexylmethyl ester, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexyl propyl (meth)acrylate, allyl glycidyl ether, etc. An epoxy group-containing monomer; 2-(methyl) acrylamide-2-methylpropane sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, sulfoethyl (meth) acrylate, and the like a monomer having a sulfonic acid group such as a sodium salt or an ammonium salt; a monomer having a phosphate group such as 2-(meth)acryloyloxyethyl hydrogen phosphate; acrolein or diacetone (meth) propylene Indoleamine, ethyl ethyl ethoxyethyl (meth) acrylate, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl Ketone-containing carbonyl-containing single Wait.

The monomer (b2) exemplified above may be used singly or in combination of two or more. Further, among the above-exemplified monomers (b2), it is preferable that (a) Methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (A) Base) 2-methoxypropyl acrylate.

In the present specification, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylic" means acrylic acid or methacrylic acid. Further, "(meth)acryloyl group means propylene fluorenyl group or methacryl fluorenyl group, and "(meth) acrylamide" means acrylamide or methacrylamide.

In the present invention, the decyl ester-containing resin (B) can be produced by a conventional polymerization method. Further, the decyl ester-containing resin (B) may be any type of copolymer as long as it is a conventional copolymer such as a random copolymer, a graft copolymer, a slanted structure copolymer or a block copolymer.

The decyl ester-containing resin (B) is obtained by, for example, copolymerizing the monomer (b1) and the monomer (b2) in the presence of a radical polymerization initiator.

The radical polymerization initiator used in the above copolymerization reaction is exemplified by, for example, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, dimethyl group. -2,2'-azobisisobutyrate and other azo compounds; benzoyl peroxide, bis(3-methylbenzhydryl) peroxide, benzamidine (3- Dimethyl peroxide compound such as methotrexate) peroxide, dilauryl peroxide; di-tert-butyl peroxide, tert-butylperoxybenzoate, third a third butyl peroxide compound such as butylperoxy isopropyl carbonate or t-butyl peroctoate; a third pentylperoxy-2-ethylhexanoate, a third pentyl group Peroxyacetic acid Ester, third amyl peroxyisodecanoate, third amyl peroxybenzoate, third amyl peroxyacetate, bis(third amyl peroxide), 1, a third pentyl peroxide compound such as 1-di(tripentylperoxy)cyclohexane; a third pentylperoxy-2-ethylhexanoate, a third hexylperoxybenzoate A third hexyl peroxide compound such as an acid ester, a third hexylperoxy-isopropyl monocarboxylate, a third hexylperoxypivalate or a third hexylperoxy neodecanoate. These polymerization initiators may be used singly or in combination of two or more.

The molecular weight of the above-described decyl ester-containing resin (B) can be adjusted by appropriately setting the amount of the polymerization initiator used and the like.

The polymerization method for obtaining the decyl ester-containing resin (B) is exemplified by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, a suspension polymerization method, and the like. Among these, a solution polymerization method is preferred from the viewpoint of easily and accurately synthesizing the above-described decyl ester-containing resin (B).

In the above copolymerization reaction, an organic solvent may also be used as needed. The organic solvent is exemplified by an aromatic hydrocarbon solvent such as xylene or toluene; an aliphatic hydrocarbon solvent such as hexane or heptane; ethyl acetate, butyl acetate; isobutyl acetate or methoxypropyl acetate; A solvent; an alcohol solvent such as isopropyl alcohol or butanol; an ether solvent such as dioxane, diethyl ether or dibutyl ether; a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone; Among these, an aromatic hydrocarbon solvent is preferred, and xylene is preferred. These solvents may be used singly or in combination of two or more.

The reaction temperature in the copolymerization reaction may be appropriately set depending on the type of the reaction initiator, and is usually in the range of 70 to 160 ° C. The temperature is preferably in the range of 80 to 140 °C. The reaction time in the above-mentioned poly-copolymerization reaction may be appropriately set depending on the reaction temperature, the type of the polymerization initiator, and the like, and is usually about 4 to 8 hours. Further, the above copolymerization reaction is preferably carried out under an atmosphere of an inert gas such as nitrogen or argon.

[Antifouling agent (C)]

The antifouling paint composition of the present invention further contains an antifouling agent (C) in addition to the above polyester resin (A) and the above decyl ester group-containing resin (B). The antifouling agent (C) can be used by a conventional one. The antifouling agent (C) is exemplified by, for example, an inorganic compound, a metal-containing organic compound, a metal-free organic compound, or the like.

The inorganic compound is exemplified by a copper compound such as cuprous oxide, copper powder, copper thiocyanate, copper carbonate, copper chloride or copper sulfate, zinc sulfate, zinc oxide, nickel sulfate or a copper-nickel alloy.

The metal-containing organic compound is exemplified by, for example, an organic copper-based compound, an organic nickel-based compound, an organic zinc-based compound, or the like, and may also be used as manne, mancozeb, or methylzinc. Propineb) and so on. The aforementioned organic copper-based compound is exemplified by, for example, oxine-copper, copper pyrithione, copper nonylphenolsulfonate, copper bis(ethylenediamine)-bis(dodecylbenzenesulfonic acid). Ester), copper acetate, copper naphthenate, bis(pentachlorophenolate) copper, and the like. The organic nickel-based compound is exemplified by nickel acetate, nickel dimethyldithiocarbamate or the like. The aforementioned organozinc compound is exemplified by, for example, zinc acetate, zinc carbazate, zinc dimethyldithiocarbamate, zinc pyrithione. (zinc pyrithione), zinc ethyl bisdithiocarbamate, and the like.

Further, the above metal-free organic compound is exemplified by, for example, N-trihalomethylthiobenzamide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amine-1 , 3-thiazole pyridine-2,4-dione, dithiocyano compound, triazine compound, and the like.

The above N-trihalomethylthiobenzamide is exemplified by, for example, N-trichloromethylthiobenzamide or N-fluorodichloromethylthiobenzamide.

The above dithiocarbamic acid is exemplified by bis(dimethylthioaminocarbamimidyl) disulfide, ammonium N-methyldithiocarbamate, and ethyl bis(dithiocarbamic acid). Ammonium, milneb, etc.

The above N-arylmaleimide is exemplified by, for example, N-(2,4,6-trichlorophenyl)maleimide, N-4-methylphenylmalamine, N-3-chlorophenyl horse.醯imine, N-(4-n-butylphenyl)maleimide, N-(anilinophenyl)maleimide, N-(2,3-dimethylphenyl)male Imine, 2,3-dichloro-N-(2',6'-diethylphenyl)maleimide, 2,3-dichloro-N-(2'-ethyl-6'- Methylphenyl) maleimide and the like.

The above 3-substituted amino-1,3-thiazolidin-2,4-dione is exemplified by, for example, 3-benzylideneamino-1,3-thiazolidine-2,4-dione, 3-(4 -methylbenzylideneamino)-1,3-thiazolidin-2,4-dione, 3-(2-hydroxybenzylideneamino)-1,3-thiazolidin-2,4-dione , 3-(4-dimethylaminobenzylideneamino)-1,3-thiazolidin-2,4-dione, 3-(2,4-dichlorobenzylideneamino)-1,3 - thiazolidine-2,4-dione and the like.

The above dithiocyano compound is exemplified as dithiocyano Alkane, dithiocyanoethane, 2,5-dithiocyanothiophene, and the like.

The above triazine-based compound is exemplified by, for example, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine.

Further, the metal-free organic compound may be, for example, 2,4,5,6-tetrachloroisophthalonitrile or N,N-dimethyldichlorophenylurea, in addition to the above-exemplified organic compound. , 5-dichloro-2-N-octyl-3-(2H)isothiazolone, N,N-dimethyl-N'-phenyl-(N-fluorodichloromethylsulfanyl)sulfonamide, Tetramethylthiuram disulfide, 3-iodo-2-propenyl butyl carbamate, 2-(methoxycarbonylamino)benzimidazole, 2,3,5,6-tetrachloro -4-(methylsulfonyl)pyridine, diiodomethyl-p-tolylhydrazide, bisdimethyldithioamine-methylenyl zinc-extended ethyl bisdithiocarbamate, phenyl (bipyridine ) bismuth dichloride, 2-(4-thiazolyl) benzimidazole, triphenylborane pyridine ‧ amine complex, medetomidine (system name: (±) 4-[1-( 2,3-Dimethylphenyl)ethyl]-1H-imidazole), dichloro-N-((dimethylamino)sulfonyl)fluoro-N-(p-tolyl)methanesulfonamide, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole, chloromethyl-n-octyl disulfide, and the like.

The antifouling agent (C) may be used singly or in combination of two or more of the above-exemplified compounds. Further, the antifouling agent (C) is preferably a cuprous oxide based on the viewpoint of exhibiting stable antifouling performance among the above-exemplified compounds, and it is preferable to use cuprous oxide and copper pyrithione in combination.

[Antifouling coating composition and coated articles]

The antifouling coating composition of the present invention contains the aforementioned polyester resin (A), The antifouling coating composition containing the decyl ester-based resin (B) and the antifouling agent (C), characterized in that the mass ratio of the polyester resin (A) to the decyl ester-containing resin (B) is 3/ In the range of from 97 to 80/20, the content of the antifouling agent (C) is in the range of 50 to 500% by mass based on the total mass of the polyester resin (A) and the decyl ester-containing resin (B). .

The mass ratio of the polyester resin (A) to the decyl ester-containing resin (B) is in the range of 3/97 to 80/20, preferably in the range of 7/93 to 60/40, more preferably Within the range of 10/90~40/60. When the mass ratio of the polyester resin (A) to the decyl ester-containing resin (B) is in the range of 3/97 to 80/20, the antifouling paint composition of the present invention can be maintained for a long period of time. The antifouling coating film is excellent in antifouling performance, and the antifouling coating film is less likely to cause coating film defects such as peeling of the coating film, foaming, and cracking. When the mass ratio of the polyester resin (A) to the decyl ester-containing resin (B) is less than 3/97 or more than 80/20, it may be difficult to maintain the antifouling performance of the obtained coating film for a long period of time.

The content of the antifouling agent (C) is in the range of 50 to 500% by mass, preferably 250 to 400% by mass based on the total mass of the polyester resin (A) and the decyl ester-containing resin (B). Within the scope. When 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, and when the content of the antifouling agent (C) is more than 500% by mass, The physical properties of the obtained coating film are lowered, and defects such as peeling or wrinkles occur.

The antifouling coating composition of the present invention is also visible in addition to the above polyester resin (A), decyl ester-containing resin (B) and antifouling agent (C). It is required to mix a pigment, a dye, a dehydrating agent, a plasticizer, a rocking agent (collapse preventing agent), an antifoaming agent, an antioxidant, the above polyester resin (A) or a resin other than the aforementioned decyl ester-based resin (B), Various components used in general coating compositions such as organic acids and solvents. These components may be used singly or in combination of two or more.

The above pigments are exemplified by coloring pigments such as iron oxide, talc, titanium oxide, yellow iron oxide, cerium oxide, calcium carbonate, barium sulfate, calcium oxide, carbon black, naphthol red, phthalocyanine blue, talc, cerium oxide, Mica pigments such as mica, clay, calcium carbonate, kaolin, alumina white, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, and zinc sulfide.

The content of the pigment in the antifouling coating composition is preferably in the range of 0.05 to 1000% by mass, more preferably 1 to 500, based on the total mass of the polyester resin (A) and the decyl ester-containing resin (B). Within the range of mass %.

The above dehydrating agent is an ingredient which contributes to improving the storage stability of the coating. Examples of the dehydrating agent include anhydrous gypsum, hemihydrate gypsum (calcined gypsum), a synthetic zeolite-based adsorbent (trade name "molecular sieve", etc.), and an orthoester (original formic acid) can also be used. Ester, methyl orthoacetate, orthoborate, etc.), phthalate esters, isocyanates, and the like. Among these, anhydrous gypsum and hemihydrate gypsum (calcined gypsum) which are inorganic dehydrating agents are preferable. Further, these dehydrating agents may be used singly or in combination of two or more kinds. Further, the content of the dehydrating agent in the antifouling coating composition can be appropriately adjusted, but it is preferably in the range of 0 to 100% by mass based on the total mass of the polyester resin (A) and the decyl ester-containing resin (B). , More preferably in the range of 0.5 to 25% by mass.

The plasticizer is a component which contributes to improvement of crack resistance, water resistance and the like of the obtained antifouling coating film. The plasticizers are exemplified by, for example, tricresyl phosphate, dioctyl phthalate, chlorinated alkane, liquid alkane, normal paraffin, chlorinated alkane, polybutene, terpene phenol, tricresyl phosphate (TCP). ), polyvinyl ethyl ether, and the like. These plasticizers may be used singly or in combination of two or more. The content of the above-mentioned plasticizer in the antifouling coating composition can be appropriately adjusted, but it is preferably in the range of 0.5 to 10% by mass based on the total mass of the polyester resin (A) and the decyl ester-containing resin (B). More preferably in the range of 1 to 5 mass%.

The antioxidant may, for example, be 2,6-di-tert-butyl-4-methylphenol or the like.

The above-mentioned shaker is exemplified by, for example, an organic wax (polyethylene wax, oxidized polyethylene wax, polyamidamine wax, guanamine wax, hydrogenated castor oil wax, etc.), an organic clay compound (an amine salt of Al, Ca, Zn, Stearate, lecithin salt, alkyl sulfonate, etc.), bentonite, synthetic fine powder cerium oxide, and the like. These shakers may be used singly or in combination of two or more. The content of the above-mentioned shaker in the antifouling coating composition can be appropriately adjusted, and is, for example, preferably in the range of 0.25 to 50% by mass based on the total mass of the polyester resin (A) and the decyl ester-containing resin (B).

In addition to the polyester resin (A) and the decyl ester-containing resin (B), the antifouling coating composition of the present invention may contain one or more other resins as needed, and the resin is listed as Acrylic resin without decyl ester group, polyacrylic acid acrylate resin, epoxy resin, fluorine Resin, polybutene resin, polyoxymethylene rubber, urethane resin, polyamide resin, vinyl chloride copolymer resin, chlorinated rubber, chlorinated olefin resin, styrene ‧ butadiene copolymer resin, Ketone resin, ethylene-vinyl acetate copolymer resin, vinyl chloride resin, alkyd resin, coumarin resin, terpene phenol resin, petroleum resin, and the like.

Further, the antifouling coating composition of the present invention may contain a conventional rosin-based compound. The rosin-based compound is exemplified by, for example, rosin, rosin derivatives, rosin metal salts, and the like. The rosin is exemplified by, for example, tall rosin, gum rosin, wood rosin, and the like. The rosin derivative is exemplified by maleated turpentine, formylated turpentine, polymeric rosin, etc., which are obtained by reacting hydrogenated rosin, rosin and maleic anhydride. The rosin metal salt is exemplified by zinc rosinate, calcium rosinate, copper rosinate, magnesium rosinate, and a reaction product of a metal compound and rosin. These rosin-based compounds may be used singly or in combination of two or more.

The amount of the rosin-based compound to be used is not particularly limited, but is preferably 50% by mass or less, and more preferably 30% by mass or less based on the total mass of the polyester resin (A) and the decyl ester-containing resin (B).

The antifouling coating composition of the invention can be formulated with an aliphatic solvent, an aromatic solvent (xylene, toluene, etc.), a ketone solvent (methyl isobutyl ketone, cyclohexanone, etc.), an ester solvent, an ether solvent (propylene glycol monomethyl An organic solvent which is a solvent for an antifouling coating is generally used, such as an ether, propylene glycol monomethyl ether acetate, or an alcohol solvent (isopropanol). Further, the amount of the organic solvent to be blended can be appropriately adjusted, for example, in such a manner that the total solid content of the antifouling paint composition is in the range of 20 to 90% by mass, or It is further added according to the workability at the time of painting.

The antifouling coating composition of the present invention can be prepared by the same method as the conventional antifouling coating composition. For example, the polyester resin (A), the decyl ester-containing resin (B), the antifouling agent (C), and optionally the aforementioned organic solvent or additive are added to the stirring tank once or sequentially, and stirred and mixed. And manufacturing.

The coated article of the present invention is an article obtained by coating the surface of a substrate with the antifouling coating composition of the present invention. The coated article may be a step of drying the antifouling coating composition covering the surface of the substrate by at least one step of applying or impregnating the antifouling coating composition onto the surface of the substrate once or several times. The manufacturing method is obtained.

The above-mentioned substrate is exemplified by a substrate which is in contact with sea water or fresh water (for example, frequently or intermittently), in particular, an underwater structure; a ship outer plate or a ship bottom; a water conduit or a cooling pipe of a power plant; Fishing nets, fishing gear or buoys made by such; rope nets and other accessories. Moreover, 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 speed) of the coating film, for example, the film thickness (μm) per coating is 30 to 250 μm/time. It is preferably about 75 to 150 μm/time, and it may be repeatedly applied twice or more as needed.

The primer, the anti-corrosive coating and the optional adhesive coating are applied on the surface of the surface of the substrate, and the antifouling coating of the invention may also be applied by brushing, spraying, rolling, dipping or the like. Composition. Further, the antifouling coating composition of the present invention can be repeatedly applied to the surface of an existing antifouling coating film. Drying of the coating film can be carried out at room temperature, or as needed Heating at a temperature of 100 ° C or more.

[Examples]

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

Manufacture of polyester resin (A) (Production Example 1) Production of Polyester Resin (A1)

527.2 parts of PA, 267.2 parts of NPG, and 269.7 parts of DEG were fed into a 2 L reaction apparatus equipped with a thermometer, a stirrer, and a rectification column, and the temperature of the contents of the reaction apparatus was raised to 160 °C. Next, the temperature was raised from 160 ° C to 230 ° C in 3 hours, and the content temperature was maintained at 230 ° C for 2 hours. Then, the rectification column was replaced with a water separator, and about 50.0 parts of xylene was fed into the reaction apparatus. The water and xylene are azeotropically removed to condense water for polycondensation. After confirming that the generated acid value of the resin was 1.0 mgKOH/g or less, the heating was stopped and cooling was started, and the mixture was diluted with xylene to obtain a polyester resin (A1) solution having a solid content of 70%. Further, the resin acid value was measured by dissolving a measurement sample of a mixed solution of toluene and isopropyl alcohol (mass ratio: 1/1) as a solvent, and titrating with an alcohol-based solution of potassium hydroxide having a concentration of 1/10 equivalent.

Here, the abbreviations of the polyester raw materials in the present specification are shown below in relation to the corresponding compounds.

PA: phthalic anhydride, iPA: isophthalic acid, AD: adipic acid, HHPA: hexahydrophthalic anhydride, EG: ethylene glycol, PG: propylene Alcohol, NPG: neopentyl glycol, 1,6-HD: 1,6-hexanediol, BEPG: 2-butyl-2-ethyl-1,3-propanediol, CHDM: 1,4-cyclohexane Dimethanol, DEG: diethylene glycol, TEG: triethylene glycol, tetra EG: tetraethylene glycol, DPG: dipropylene glycol, TMP: trimethylolpropane, G: glycerol, PE: pentaerythritol

(Production Examples 2 to 12, 16, and 17) Production of Polyester Resins (A2) to (A12), (A16), and (A17)

The polyester resin (A2) to (A12), (A16), ( Resin solution of A17). Further, in Production Example 17, since the acid value of the produced polyester resin was difficult to be 1.0 mgKOH/g or less, the reaction was terminated at a slightly higher acid value.

(Production Example 13) Production of Polyester Resin (A13)

377.8 parts of iPA, 364.2 parts of BEPG, and 227.6 parts of TEG were fed into a 2 L reaction apparatus equipped with a thermometer, a stirrer, and a rectification column, and the temperature of the contents of the reaction apparatus was raised to 160 °C. Next, the temperature was raised from 160 ° C to 230 ° C in 3 hours, and the content temperature was maintained at 230 ° C for 2 hours. Then, the rectification column was replaced with a water separator, and about 50.0 parts of xylene was fed into the reaction apparatus. The water and xylene are azeotropically removed to condense water for polycondensation. After confirming that the generated resin acid value was 1.0 mgKOH/g or less, the content temperature was cooled to 160 °C. Further, 112.3 parts of PA was added, and after adding at 160 ° C for 1 hour, an addition reaction (half esterification) was started, and then cold was started. but. After cooling to 130 ° C, xylene was added and diluted to obtain a resin solution of a polyester resin (A13) having a solid content of 70%.

(Production Example 14) Production of Polyester Resin (A14)

The resin solution of the polyester resin (A14) having a solid content of 70% was obtained in the same manner as in Production Example 13, except that the acid component and the alcohol component in the production example 13 were prepared as shown in Table 1.

(Production Example 15) Production of Polyester Resin (A15)

237.5 parts of PA, 29.3 parts of EG, 198.2 parts of PE, 602.6 parts of soybean oil fatty acid, and 50.0 parts of xylene were fed into a 2L reaction apparatus equipped with a thermometer, a stirrer, and a water separator to make the contents of the reaction apparatus The temperature was raised to 160 ° C for 1 hour. Next, the temperature was raised from 160 ° C to 240 ° C in 4 hours, and the condensation water formed was removed at 240 ° C to carry out polycondensation. After confirming that the resin acid value was 3.0 mgKOH/g, the heating was stopped and cooling was started, and xylene was added and diluted to obtain a resin solution of a polyester resin (A15) 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 the above respective production examples are shown in Table 1 together with the blending amounts of the production examples.

Manufacture of decyl ester-containing resin (B) (Production Example 18) Production of a decyl ester-containing resin (B1)

After feeding 40 parts of xylene into a flask equipped with a stirrer, the liquidus temperature was maintained at 140 ° C, and the amount of each monomer of each unsaturated monomer described in Table 2 was polymerized from the peroxide system within 3 hours. A mixture of 1 part of the starting agent "PERBUTYL I" (trade name, manufactured by Nippon Oil Co., Ltd.) was added dropwise to the flask. After the completion of the dropwise addition, it was kept at the same temperature for 30 minutes. Next, 10 parts of xylene and 1 part of "PERBUTYL I" were added dropwise over 20 minutes, and after continuous stirring at the same temperature for 2 hours, the liquid phase was cooled. The resin solution was prepared by adding xylene to the flask so that the solid content concentration of the produced resin was 50% by mass, and a resin solution containing the decyl ester-based resin (B1) was obtained.

(Production Examples 19 and 20) Production of decyl ester-based resins (B2) and (B3)

A resin solution containing a decyl ester-based resin (B2) and (B3) was obtained in the same manner as in Production Example 18 except that the unsaturated monomer in Production Example 18 was blended as shown in Table 2 (solid content concentration: 50% by mass) .

Modulation and various tests of antifouling coating compositions (Examples 1 to 23) and (Comparative Examples 1 to 5) Evaluation

The resin solution of the mixed polyester resin (A1) to (A17) and the resin solution containing the decyl ester-based resin (B1) to (B3), the antifouling agent, and the pigment are formulated as shown in Tables 3-1 and 3-2. Etc., using a homogenizer to mix and disperse at a stirring speed of about 2,000 rpm. After the dispersion, DISPARION A630-20XN (manufactured by Nanben Chemical Co., Ltd., a sag preventing agent) and a solvent were added, and the coating compositions (E1) to (E28) were prepared by dispersion stirring. Modulated coating group The product was provided in the following antifouling performance test, adhesion test and crack resistance test. The results of these tests are shown in Tables 4 to 6.

<Antifouling performance test>

The epoxy-based rust-proof paint was spray-coated on both surfaces of a sandblasted steel sheet (100 mm × 300 mm × 2 mm) so as to have a dry film thickness of 200 μm, and the epoxy-based adhesive was applied so that the dry film thickness became 100 μm. Coatings. Each of the above coating compositions was applied to both sides of the coated plate four times by spray coating so that the dry film thickness became 480 μm on one side, and dried in a constant temperature and humidity chamber at a temperature of 20 ° C and a humidity of 75% for one week. , making test strips. Using this test piece, seawater immersion was carried out for 48 months in Owase Bay, Mie Prefecture, and the ratio (attached area) of the area occupied by the attached organism on the test coating film was measured over time.

◎: (qualified) no attached organisms were observed

○: (Qualified) The area occupied by attached organisms is less than 5%

△: (failed) The occupied area of the attached organism is 5% or more and less than 30%.

×: (failed) The occupied area of the attached organism is 30% or more

<Adhesion test>

Spray-coated steel plate (120 mm × 120 mm × 1 mm) which is bendable and can be mounted on a cylindrical drum (diameter: 500 mm × height: 240 mm) so that the epoxy-based rust-proof paint becomes a dry film thickness of 200 μm. ), in order to make the dry film thickness 100 μm Apply epoxy adhesive coating. Each of the above coating compositions was applied to the coated steel sheet four times by spray coating so that the dry film thickness became 480 μm on one side, and dried at a constant temperature and humidity chamber at a temperature of 20 ° C and a humidity of 75%. One week, a test piece was produced. The test piece was placed in the above-mentioned cylindrical drum, and the cylindrical drum was rotated at 60 knots for 24 months under 500 mm from the sea surface of the Bay of Hyogo. The test piece was recovered from seawater over time, and a checkerboard test of 5 mm intervals was carried out. The evaluation is based on ISO 2409:1992.

◎: (Qualified) Table Classification (Tablel Classification) 0‧1

○: (Qualified) Table Category 2

△: (failed) table classification 3

×: (failed) table classification 4‧5

<Cracking resistance test>

The coating film of the test piece for the above adhesion test was visually observed to investigate whether or not cracking occurred.

◎: (passed) no cracks were observed

○: (passed) a part of the surface of the coating film was observed to be finely cracked.

△: (failed) fine or clear cracks were observed on a wide range of coating film surfaces

×: (failed) Observed cracks reaching the base

Claims (6)

An antifouling coating composition comprising an antifouling coating composition comprising a polyester resin (A), a decyl ester-based resin (B) and an antifouling agent (C), characterized by: the decyl ester-containing resin ( B) is derived from the general formula (I): R ⁵ -CH=C(R ⁴ )-COO-SiR ¹ R ² R ³ . . . (I) In the formula (I), 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 ³ represents a hydrogen atom or R ⁶ -O-CO- (only, R ⁶ is an organic group or an alkyl group represented by -SiR ⁷ R ⁸ R ⁹ , and R ⁷ , R ⁸ and R ⁹ each independently represent one or more of the monomers (b1) represented by the hydrocarbon group], and A copolymer of one or more monomers (b2) other than the monomer (b1), wherein the mass ratio of the polyester resin (A) to the decyl ester-containing resin (B) is 3/97. In the range of -80/20, the content of the antifouling agent (C) is 50 to 500% by mass based on the total mass of the polyester resin (A) and the decyl ester-containing resin (B). Within the scope. The antifouling coating composition according to the first aspect of the invention, wherein the polyester resin (A) has an acid value in the range of 0 to 120 KOHmg/g. The antifouling coating composition according to claim 1 or 2, wherein the polyester resin (A) has a weight average molecular weight of 15,000 or less. The antifouling coating composition according to any one of claims 1 to 3, wherein the polyester resin (A) and the aforementioned decyl ester-containing resin The mass ratio of (B) is in the range of 7/93 to 60/40. The antifouling coating composition according to any one of claims 1 to 4, wherein the decyl ester-containing resin (B) is a mass ratio of the monomer (b1) to the monomer (b2) ( B1)/(b2) is in the range of 20/80 to 70/30. A coated article, which is characterized in that the article to be coated is coated with an antifouling coating composition according to any one of claims 1 to 5.