KR102470397B1 - Antifouling Coating Material Composition and Coated Article Coated with Same - Google Patents

Abstract

The present invention provides an antifouling coating composition capable of forming an antifouling coating film capable of maintaining excellent antifouling property for a long period of time and hardly causing coating film defects such as peeling, blisters, and cracks, and an antifouling coating composition thereof for fishing nets , It is an object of the present invention to provide a painted article obtained by painting a coated object such as a ship, marine or coastal structure. The present invention is an antifouling coating composition containing a specific polyester resin (A), a resin containing a silyl ester group (B) and an antifouling agent (C), and a coated article coated with the composition.

Description

Antifouling coating composition, and coated article obtained by painting the same {Antifouling Coating Material Composition and Coated Article Coated with Same}

The present invention relates to an antifouling coating composition and a painted article obtained by coating the same, and more particularly, to an antifouling coating composition capable of forming an antifouling coating film capable of maintaining excellent antifouling property for a long period of time, and an antifouling coating composition thereof It relates to a painted article obtained by painting on an object to be coated.

Recently, as a resin for antifouling paints in place of organotin-containing copolymers that are concerned about marine pollution, various resins for antifouling paints in which ester bonds hydrolyzed in seawater are introduced into the side chains of polymers have been studied. Among them, in the antifouling coating composition using a resin containing a trialkylsilyl ester group, since the trialkylsilyl ester moiety is hydrolyzed in seawater, the coating film obtained from the antifouling coating composition has a property of gradually dissolving in seawater from the surface, thereby preventing contamination. It has reached practical use as a resin for anti-corrosive paints.

Such trialkylsilyl ester group-containing resins differ in the rate of dissolution of the coating film depending on the structure of the trialkylsilyl ester group. For example, in antifouling coating compositions using tri-n-butylsilylester group-containing resins, it is difficult to maintain the antifouling performance of the coating film for a long period of time because the coating film obtained has a high dissolution rate. On the other hand, an antifouling coating composition using a resin containing a triorganosilyl ester group in which a branched alkyl group is bonded to a silicon atom has a slow dissolution rate of the obtained coating film, so that aquatic fouling organisms are not affected in sea areas with low sea water temperatures. There was a problem that it was easy to attach. Therefore, in the latter antifouling coating composition, a method of controlling the dissolution rate of the coating film by adding rosin or a rosin derivative has been studied (Patent Documents 1 to 3). However, even in such a method, if the amount of rosin or rosin derivative used is small, the solubility of the coating film in seawater is not sufficiently obtained, and there is a problem that the antifouling effect is difficult to sustain. On the other hand, if the amount of rosin or rosin derivative used is large, the dissolution rate of the coating film increases and the antifouling effect is improved, but the physical properties and adhesiveness of the coating film deteriorate, making it difficult to maintain the antifouling effect for a long time, resulting in peeling of the coating film and blistering. , there was a tendency for coating film defects such as cracks to occur easily.

Patent Document 1: Japanese Laid-Open Patent Publication No. 10-30071 Patent Document 2: Japanese Unexamined Patent Publication No. 2002-53797 Patent Document 3: Japanese Unexamined Patent Publication No. 2011-26357

An object of the present invention is to provide an antifouling coating composition capable of forming an antifouling coating film capable of maintaining excellent antifouling properties over a long period of time and hardly causing coating film defects such as peeling, blisters, and cracks, and antifouling thereof To provide a painted article formed by coating a paint composition on a target object such as a fishing net, a ship, a marine or coastal structure, and the like.

The inventors of the present invention conducted intensive studies to achieve the above object, and a coating film obtained by an antifouling coating composition containing a specific polyester resin and a silyl ester group-containing resin can control the dissolution rate of the coating film into the sea, and at the same time Since the physical properties of the coating film, such as maintaining excellent antifouling property over a long period of time, are excellent, when the above-described antifouling paint composition is coated on the bottom of a ship, separation of the coating film during navigation or anchorage, It has been found that coating film defects such as blisters and cracks are less likely to occur. The present invention was completed based on this knowledge.

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

Item 1. An antifouling paint composition comprising a polyester resin (A), a silyl ester group-containing resin (B) and an antifouling agent (C), wherein the silyl ester group-containing resin (B) is of the general formula (I):

[In formula (I), R ⁴ represents a hydrogen atom or a methyl group, R ¹ , R ² and R ³ each independently represents a hydrocarbon group, R ⁵ is 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); and a copolymer of one or two or more monomers (b2) other than the monomer (b1), wherein the mass ratio between the polyester resin (A) and the silyl ester group-containing resin (B) is 3/ within the range of 97 to 80/20, and the content of the antifouling agent (C) is 50 to 500 mass% based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B) The antifouling paint composition, characterized in that within the range.

Item 2. The antifouling paint composition according to Item 1, wherein the acid value of the polyester resin (A) is in the range of 0 to 120 KOHmg/g.

Item 3. The antifouling coating composition according to Item 1 or Item 2, wherein the polyester resin (A) has a weight average molecular weight of 15000 or less.

Item 4. The antifouling coating composition according to any one of Items 1 to 3, wherein the mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 7/93 to 60/40.

Item 5. The mass ratio (b1)/(b2) of the monomer (b1) to the monomer (b2) in the silyl ester group-containing resin (B) according to any one of Items 1 to 4 is 20/80. An antifouling coating composition within the range of ~70/30.

Item 6. A coated article obtained by coating the antifouling coating composition according to any one of Items 1 to 5 on an object to be coated.

The antifouling coating composition of the present invention can maintain excellent antifouling properties over a long period of time, and can form a coating film in which coating film defects such as peeling, blisters, and cracks are less likely to occur.

The antifouling paint composition of the present invention is an antifouling paint composition comprising a polyester resin (A), a silyl ester group-containing resin (B), and an antifouling agent (C), wherein the silyl ester group-containing resin (B), General Formula (I):

[In formula (I), R ⁴ represents a hydrogen atom or a methyl group, R ¹ , R ² and R ³ each independently represents a hydrocarbon group, R ⁵ is 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); and a copolymer of one or two or more monomers (b2) other than the monomer (b1), wherein the mass ratio between the polyester resin (A) and the silyl ester group-containing resin (B) is 3/ within the range of 97 to 80/20, and the content of the antifouling agent (C) is 50 to 500 mass% based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B) It is characterized by being within the range. 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 paint composition of the present invention uses acid component (a1) and alcohol component (a2) as main raw materials, and by esterification reaction and/or transesterification reaction of each of these components can be manufactured

acid component (a1)

In this invention, the acid component (a1) can use the acid component normally used for manufacture of a polyester resin. 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 esters, anhydrides and halides of these acids. can

As the alicyclic polybasic acid, generally, compounds having one or more alicyclic structures (mainly 4 to 6 membered rings) and two or more carboxyl groups in one molecule, and acid anhydrides, esters and halides of the compounds can be used. . Examples of such alicyclic polybasic acids include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 2-cyclohexene-1,2- Dicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, tetrahydromethylbutyric acid, 3-methyl-1,2-cyclohexanedicarboxylic acid alicyclic polycarboxylic acids such as 4-methyl-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanedicarboxylic acid, and 1,3,5-cyclohexanedicarboxylic acid; anhydrides of these alicyclic polyvalent carboxylic acids; lower alkyl esters of these alicyclic polycarboxylic acids and the like, and these may be used alone or in combination of two or more.

As the aliphatic polybasic acid, generally, 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. Examples of such aliphatic polybasic acids include succinic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, aliphatic polycarboxylic acids such as brassic acid, octadecanedioic acid, and citric acid; anhydrides of these aliphatic polycarboxylic acids; Halogenation of these aliphatic polycarboxylic acids, etc. are mentioned, These can be used individually or in combination of 2 or more types.

As the aromatic polybasic acid, generally, an aromatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aromatic compound, an ester product of the aromatic compound, and a halide of the aromatic compound can be used.

As an aromatic polybasic acid which has two carboxyl groups in 1 molecule, For example, Aromatic polyhydric carboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, and 4,4'-biphenyl dicarboxylic acid; and anhydrides of these aromatic polycarboxylic acids.

As an aromatic polybasic acid which has three or more carboxyl groups in 1 molecule, a trivalent aromatic polyhydric carboxylic acid, a tetravalent aromatic polyhydric carboxylic acid, etc. are mentioned, for example. Examples of the trivalent aromatic polycarboxylic acids include trimellitic acids such as trimellitic acid, trimellitic anhydride, trimellitic acid alkyl esters and trimellitic acid halides; hemimeritic acids, such as hemimeritic acid, hemimeritic anhydride, hemimeritic acid alkyl esters, and hemimeritic acid halides; trimesic acids such as trimesic acid, trimesic acid alkyl esters and trimesic acid halides; Various naphthalene tricarboxylic acids and their anhydrides having different carboxyl group bonding positions to aromatic rings; various anthracyctriconic acids and anhydrides thereof in which the carboxyl group is different in the bonding position to the aromatic ring; various biphenyltricarboxylic acids and anhydrides thereof in which the bonding position of the carboxyl group to the aromatic ring is different; various benzophenone tricarboxylic acids and their anhydrides having different carboxyl group bonding positions to aromatic rings; Ethylene bistrimeritic acid, its anhydride, etc. are mentioned. Examples of the tetravalent aromatic polycarboxylic acids include pyromellitic acids such as pyromellitic acid, pyromellitic dianhydride, pyromellitic acid alkyl ester, and pyromellitic acid halide; mellophanic acids such as mellophanic acid, mellophanic acid dianhydride, mellophanic acid alkyl esters, and mellophanic acid halides; and prenitic acids such as prehnitic acid, prenitic acid anhydride, prenitic acid alkyl ester, and prenitic acid halide. These aromatic polybasic acids can be used alone or in combination of two or more.

In the present invention, monocarboxylic acids such as aromatic monocarboxylic acids, aliphatic monocarboxylic acids, and alicyclic monocarboxylic acids may be used as the acid component (a1) used in the production of the polyester resin (A). Examples of aromatic monocarboxylic acids include benzoic acid, methyl benzoic acid, ethyl benzoic acid, p-t-butyl benzoic acid, naphthalene carboxylic acid, salicylic acid, 4-methyl benzoic acid, 3-methyl benzoic acid, phenoxy acetic acid, and biphenyl carboxylic acid. can be heard Examples of aliphatic monocarboxylic acids include acetic acid, lactic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, caprylic acid, ferrgonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, Palmitic acid, stearic acid, oleic acid, elaidic acid, brassidic acid, linoleic acid, linolenic acid, rosin acid, palm oil fatty acid, cottonseed oil fatty acid, marsh oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, sesame oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, and saturated or unsaturated aliphatic monocarboxylic acids such as rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, and birdflower oil fatty acid, which may be used alone or in combination of two or more.

Examples of the alicyclic monocarboxylic acid include cyclohexanecarboxylic acid, cyclopentanecarboxylic acid, cycloheptanecarboxylic acid, 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, and 4-laurylcyclohexanecarboxylate. This acid etc. are mentioned, These can be used individually or in combination of 2 or more types.

In this invention, the acid component (a1) used for manufacture of a polyester resin (A) may contain esterification products, such as the glycerol ester of the said monocarboxylic acid. Examples of glycerin esters of monocarboxylic acids include coconut oil, cottonseed oil, horse oil, rice bran oil, fish oil, sesame oil, soybean oil, linseed oil, tung oil, rapeseed oil, castor oil, dehydrated castor oil, and birdflower oil. have.

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

Alcohol component (a2)

In this invention, the alcohol component (a2) can use the alcohol component normally used for manufacture of a polyester resin. As such an alcohol component, it is preferable to include dihydric alcohols such as alicyclic diols, aliphatic diols, and aromatic diols and/or trihydric or higher polyhydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, Tetraethylene glycol, pentaethylene glycol, 1,2-propylene glycol, di-1,2-propylene glycol, tri-1,2-propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 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-hexanediol, 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-phenyl Propane-1,3-diol, 1,3-propylene glycol, 1,3-butylene glycol, 2-ethyl-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-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate (esterified product of hydroxypivaric acid and neopentyl glycol), bisphenol A, Bisphenol F, alkylene oxide adduct of pisphenol A, bis(4-hydroxyhexyl)-2,2-propane, bis(4-hydroxyhexyl)methane, 3,9-bis(1,1-dimethyl- Esterdiol compounds such as 2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, bis(hydroxyethyl)terephthalate, diethylene glycol, triethylene glycol, glycerin, Diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris(2-hydroxyethyl ) Isocyanurates, polylactone polyol compounds obtained by adding lactone compounds such as ε-caprolactone to these polyhydric alcohols, and the like and these can be used individually or in combination of 2 or more types, respectively.

Also, if necessary, methanol, ethanol, propyl alcohol, n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol , monoalcohols such as benzyl alcohol, stearyl alcohol, 2-phenoxyethanol, and dodecyl alcohol; An alcohol compound obtained by reacting a compound having a protonic acid with a monoepoxy compound such as ethylene oxide, propylene oxide, butylene oxide, glycidyl ester of synthetic high branched saturated fatty acids (trade name 'Cadura E10' manufactured by Hexion Specialty Chemicals) ; Metal-containing alcohol compounds, such as zinc lactate, etc. can also be used as an auxiliary raw material at the time of manufacturing polyester resin (A).

In the present invention, the method for producing the polyester resin (A) is not particularly limited, and a conventional method can be employed. The polyester resin (A), for example, is prepared by mixing one or two or more acid components (a1) and one or two or more alcohol components (a2) in a nitrogen stream at a temperature of 150 to 250°C for 2 to 10 hours. It can be manufactured by making it react and carrying out an esterification reaction and/or a transesterification reaction. In the above esterification reaction and/or transesterification reaction, the acid component (a1) and the alcohol component (a2) may be added at once or may be added in several times. The reaction may be carried out in the presence of a known organic solvent.

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

And, in the esterification reaction and/or transesterification reaction, a catalyst may be used to promote the reaction. Examples of such catalysts include dibutyltin oxide, antimony trioxide, iron acetate, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, tetraisopropyl titanate, zinc borate, and zinc chloride. , 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 esterification and/or transesterification of the acid component (a1) and the alcohol component (a2) as main raw materials. Known organic and/or inorganic compounds other than constituents derived from the acid component (a1) and the alcohol component (a2) may be included as constituents, and amidation reaction, urethanation reaction, imidation reaction, carbonate It may be manufactured with known chemical reactions such as conversion reaction and urea reaction. For example, the polyester resin (A) is an organic acid zinc, organic acid copper, zinc chloride, copper chloride, zinc hydroxide, copper hydroxide, a reaction intermediate or a reaction product during or after the reaction of the esterification reaction and / or transesterification reaction. , metal compounds such as zinc oxide and copper oxide, fatty acids, fats and oils, mono- or polyisocyanate compounds, mono- or polyamine compounds having hydrogen-bonded nitrogen, epoxy compounds, acrylic resins, vinyl ester resins, etc. may be modified polyester resins obtained by reacting .

In the polyester resin (A), the constituent components derived from the acid component (a1) and the alcohol component (a2) are preferably 80 mol% or more of the total constituents of the resin, and more preferably 90 mol% or more. do.

In addition, the resin acid value of the polyester resin (A) is preferably in the range of 0 to 120 mgKOH/g, and more preferably in the range of 0 to 95 mgKOH/g, from the viewpoint of maintaining the antifouling property of the obtained coating film over a long period of time. And, it is particularly preferred that within the range of 0 ~ 45mgKOH / g.

Furthermore, the weight average molecular weight of the polyester resin (A) is preferably 15,000 or less, more preferably within the range of 190 to 7000, from the viewpoint of antifouling properties of the obtained coating film and maintaining the antifouling properties over a long period of time, , It is particularly preferably within the range of 500 to 4,000.

In the present specification, the weight average molecular weight is a value obtained by converting the 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 (product reviews 'TSKgel G-4000HXL', 'TSKgel G-3000HXL', 'TSKgel G-2500HXL' and 'TSKgel G-2000HXL') (all manufactured by Tosoh Co., Ltd.) were used. So, the mobile phase; tetrahydrofuran, measured temperature; 40° C., flow rate; 1 ml/min, detector; It can be done under the condition of RI.

[Silyl ester group-containing resin (B)]

The antifouling coating composition of the present invention further includes a silyl ester group-containing resin (B) in addition to the polyester resin (A). The silyl ester group-containing resin (B) is a monomer (b1) having a polymerizable unsaturated group represented by the following general formula (I) and a triorganosilyl ester group (hereinafter sometimes referred to as "monomer (b1)") It consists of 1 type or 2 or more types of copolymers of 1 type, or 2 or more types, and the monomer (b2) which has a polymerizable unsaturated group other than the said monomer (b1), Preferably the weight average molecular weight (Mw) is 1,000-150,000 It is within the range of, and more preferably, the weight average molecular weight (Mx) is within the range of 3,000 to 80,000.

[In formula (I), R ⁴ represents a hydrogen atom or a methyl group, R ¹ , R ² and R ³ each independently represents a hydrocarbon group, R ⁵ is 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 each of R ⁷ , R ⁸ and R ⁹ independently represents a hydrocarbon group)]

When the Mw of the silyl ester group-containing resin (B) used in the antifouling coating composition of the present invention is less than 1,000, the dissolution rate of the coating film obtained from the antifouling coating composition increases, but the physical properties of the coating film deteriorate, resulting in blisters or cracks There are cases where this becomes more likely to occur. In addition, when the Mw of the silyl ester group-containing resin (B) exceeds 150,000, the dissolution rate of the coating film obtained from the antifouling paint composition may be reduced, resulting in poor antifouling properties.

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

In addition, R ⁴ , R ¹ , R ² and R ³ in the formula (I-1) are the same as R ⁴ , R ¹ , R ² and R ³ in the formula (I), respectively.

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

Examples of the monomer represented by the formula (I-1) (hereinafter referred to as “monomer (b1-1)”) include trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, and triiso (meth)acrylate. (meth)acrylate trialkylsilyl such as propylsilyl; desirable.

In the monomer (b1), R ⁵ in the formula (I) is '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), represented by the following general formula (I-2).

Meanwhile, R ⁴ , R ¹ , R ² and R ³ in formula (I-2) are the same as R ⁴ , R ¹ , R ² and R ³ in formula (I) or formula (I-1), respectively. do.

As the organic group for R ⁶ in the formula (I), the formula (I-1) or the formula (I-2), a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, An unsaturated alkyl group, an aralkyl group, etc. are mentioned.

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

Moreover, as said cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group etc. are mentioned, for example.

As said unsaturated alkyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group etc. are mentioned.

As said aralkyl group, a benzyl group, a phenethyl group, a phenylpropyl group etc. are mentioned, for example.

On the other hand, the said alkyl group, cycloalkyl group, an unsaturated alkyl group, and an aralkyl group may have a substituent. As such a substituent, an alkoxy group, an acyl group, etc. are mentioned, for example. In addition, the number of substituents, the position of substitution, etc. are not particularly limited as long as the effect of the present invention is not hindered.

Examples of the monomer represented by the formula (I-2) (hereinafter referred to as “monomer (b1-2)”) include a maleic acid diester compound and a fumaric acid diester compound (R ⁴ in the formula (I-2) is hydrogen atoms) and the like.

The hydrocarbon group for R ⁷ , R ⁸ and R ⁹ in the formula (I), the formula (I-1) or the formula (I-2) has a linear or branched chain having 1 to 10 carbon atoms. It is preferably an alkyl group or an unsubstituted or substituted phenyl group with an arbitrary substituent, and each hydrocarbon group may be the same or different. Among them, an alkyl group having 1 to 5 carbon atoms is preferable, and an alkyl group such as methyl, ethyl, propyl, n-butyl, s-butyl, t-butyl or isopropyl is particularly preferable.

The monomer (b1) is preferably an isopropylsilyl group-containing unsaturated monomer in view of the solubility of the obtained coating film, the durability of antifouling performance, and the difficulty of generating blisters or cracks. Examples of such an isopropylsilyl group-containing unsaturated monomer include triisopropylsilyl (meth)acrylate, triisopropylsilyl 4-pentenoate, bis(triisopropylsilyl) maleate, triisopropylsilyl maleate, and maleic acid. Ethyltriisopropylsilyl, maleate n-butyltriisopropylsilyl, maleate isobutyltriisopropylsilyl, maleate t-butyltriisopropylsilyl, maleate n-pentyltriisopropylsilyl, maleate isopentyltriisopropylsilyl , 2-ethylhexyltriisopropylsilyl maleate, cyclohexyltriisopropylsilyl maleate, bis(triisopropylsilyl) fumarate, methyl triisopropylsilyl fumarate, ethyl triisopropylsilyl fumarate, n-butyl fumarate Triisopropylsilyl, isobutyltriisopropylsilyl fumarate, n-pentyltriisopropylsilyl fumarate, isopentyltriisopropylsilyl fumarate, 2-ethylhexyltriisopropylsilyl fumarate, cyclohexyl fumarate Triisopropylsilyl etc. are mentioned, In particular, triisopropylsilyl (meth)acrylate is preferable. In addition, these triisopropylsilyl group containing monomers can be used individually or in combination of 2 or more types.

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

When the mass ratio (b1)/(b2) is less than 20/80, the dissolution rate of the obtained coating film is slow and the antifouling performance may be poor. When the mass ratio (b1)/(b2) is greater than 70/30, , the solubility of the obtained coating film increases, but it may become difficult to maintain the antifouling effect over a long period of time.

Examples of monomer (b2) copolymerizable with monomer (b1) (or monomer (b1-1) and/or (b1-2)) include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylate. alkyl (meth)acrylates such as n-butyl acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and 2-ethoxyethyl (meth)acrylate; Ethylene glycol monomethyl (meth)acrylate, (meth)acrylate having a polyoxyethylene chain at one end of which is an alkoxy group, (meth)acrylate having a polyoxypropylene chain at one end of which is an alkoxy group, (meth)acrylate (meth)acrylic acid alkylene glycol monomethyls such as propylene glycol monomethyl acrylate; ε of monoesters of (meth)acrylic acid and dihydric alcohols having 2 to 8 carbon atoms -Hydroxyalkyl (meth)acrylates of hydroxyl group-containing monomers, such as caprolactone denatured products, aryl alcohols, and (meth)acrylates having a polyoxyethylene chain with a hydroxyl group at the molecular end; (meth)acrylonitrile, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, (meth)acryloylmorpholine, N-isopropyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide ) Acrylamide, N-alkoxymethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate ) Nitrogen-containing monomers such as adducts of acrylamide and glycidyl (meth)acrylate with 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; vinyltoluene; (alpha)-methylstyrene etc. are mentioned. 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 β-carboxyethyl (meth)acrylate; Glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3 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 sodium or ammonium salts thereof; monomers having phosphoric acid groups such as 2-(meth)acryloyloxyethyl acid phosphate; Carbonyl groups such as acrolein, diacetone (meth)acrylamide, acetacetoxyethyl (meth)acrylate, and vinylalkyl ketones having 4 to 7 carbon atoms (eg, vinylmethyl ketone, vinylethyl ketone, and vinylbutyl ketone). A containing monomer etc. can also be used.

The monomers (b2) exemplified above can be used alone or in combination of two or more. In addition, among the monomers (b2) exemplified above, particularly methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and 2-methoxy (meth)acrylate Ethyl, (meth)acrylic acid 2-methoxypropyl, etc. are preferable.

Meanwhile, 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 (B) can be produced by a known polymerization method. On the other hand, the silyl ester group-containing resin (B) may be any type of copolymer as long as it is a known copolymer such as a random copolymer, a graft copolymer, a gradient structure type copolymer, or a block copolymer.

The silyl ester group-containing resin (B) is 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, azo compounds such as 2'-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-amylperoxy-2-ethylhexanoate, t-amylperoxyacetate, t-amylperoxyisononanoate, t-amylperoxybenzoate, t-amylperoxyacetate, di(t-amylfer oxide), t-amyl peroxide compounds such as 1,1-di(t-amylperoxy)cyclohexane; t-hexylperoxy-2-ethylhexanoate, t-hexylperoxybenzoate, t-hexylperoxy-isopropyl monocarbonate, t-hexylperoxypivalate, t-hexylperoxyneodecanoate, etc. of t-hexyl peroxide compounds, and the like. These polymerization initiators can be used individually or in combination of 2 or more types.

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

Examples of the polymerization method for obtaining the silyl ester group-containing resin (B) include solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization. Among these, the solution polymerization method is particularly preferable in that the silyl ester group-containing resin (B) can be simply and precisely synthesized.

In the above copolymerization reaction, you may use an organic solvent as needed. Examples of such an organic solvent include aromatic hydrocarbon-based solvents such as xylene and toluene; aliphatic hydrocarbon-based solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, 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. Among these, aromatic hydrocarbon solvents are preferred, and xylene is particularly preferred. These solvents can be used individually or in combination of 2 or more types.

The reaction temperature in the above copolymerization reaction may be appropriately set depending on the type of polymerization initiator, etc., 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 appropriately set according to the reaction temperature or the type of polymerization initiator, and is usually about 4 to 8 hours. Moreover, it is preferable that the said copolymerization reaction is performed in the atmosphere of an inert gas, such as nitrogen gas and argon gas.

[Anti-fouling agent (C)]

The antifouling coating composition of the present invention further includes an antifouling agent (C) in addition to the polyester resin (A) and the silyl ester group-containing resin (B). As the antifouling agent (C), conventionally known ones can be used. Examples of the antifouling agent (C) include inorganic compounds, metal-containing organic compounds, and metal-free organic compounds.

Examples of the inorganic compound include copper zincate, copper powder, copper thiocyanate, copper carbonate, copper chloride and copper sulfate, zinc sulfate, zinc oxide, nickel sulfate, copper-nickel alloy, and the like.

Examples of the metal-containing organic compound include organic copper compounds, organic nickel compounds, and organic zinc compounds, and manneb, manseb, propineb, and the like can also be used. Examples of the organic copper compound include copper auxin, copper pyrithione, copper nonylphenolsulfonate, copper bis(ethylenediamine)-bis(dodecylbenzenesulfonate), copper acetate, copper naphthenate, and bis(pentachlorophenolic acid). and the like. Examples of the organic nickel-based compound include nickel acetate and nickel dimethyldithiocarbamate. Examples of the organic zinc compound include zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, zinc pyrithione, and zinc ethylenebisdithiocarbamate.

In addition, examples of organic compounds not containing the above metals include N-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, and 3-substituted amino-1,3-thiare. A zolidine-2,4-dione, a dithiocyano type compound, a triazine type compound, etc. are mentioned.

Examples of the N-trihalomethylthiophthalimide include N-trichloromethylthiophthalimide and N-fluorodichloromethylthiophthalimide.

Examples of the dithiocarbamic acid include bis(dimethylthiocarbamoyl)disulfide, ammonium N-methyldithiocarbamate, ammonium ethylenebis(dithiocarbamic acid), and Milneb.

Examples of the N-arylmaleimide include N-(2,4,6-trichlorophenyl)maleimide, N-4-triylmaleimide, N-3-chlorophenylmaleimide, and N-(4-n -Butylphenyl) maleimide, N- (anilinophenyl) maleimide, N- (2,3-xylyl) maleimide, 2,3-dichloro-N- (2', 6'-diethylphenyl) maleimide mid, 2,3-dichloro-N-(2'-ethyl-6'-methylphenyl) maleimide, and the like.

Examples of the 3-substituted amino-1,3-thiazolidine-2,4-dione include 3-benzylideneamino-1,3-thiazolidine-2,4-dione and 3-(4-dione). Methylbenzylideneamino)-1,3-thiazolidine-2,4-dione, 3-(2-hydroxybenzylideneamino)-1,3-thiazolidine-2,4-dione, 3-(4 -Dimethylaminobenzylideneamino)-1,3-thiazoline-2,4-dione, 3-(2,4-dichlorobenzylideneamino)-1,3-thiazolidine-2,4-dione, etc. can

Examples of the dithiocyano-based compounds include dithiocyanomethane, dithiocyanoethane, and 2,5-dithiocyanothiophene.

As said triazine type compound, 2-methylthio- 4-t- butylamino 6-cyclopropylamino- s-triazine etc. are mentioned, for example.

In addition, organic compounds that do not contain the above metals, in addition to the organic compounds exemplified above, include, for example, 2,4,5,6-tetrachloroisophthalonitrile, N,N-dimethyldichlorophenyl urea, 4,5- Dichloro-2-N-octyl-3-(2H)isothiazolone, N,N-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfamide, tetramethylthiuramdisulfide, 3-iodine -2-propynylbutylcarbamate, 2-(methoxycarbonylamino)benzimidazole, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, diiodomethylparatrilsulfone, Bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, phenyl (bispyridine)bismasdichloride, 2-(4-thiazoyl)benzimidazole, triphenylboronpyridine amine complex, medetomidine (system Name: (±)4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole), dichloro-N-((dimethylamino)sulfonyl)fluoro-N-(p-tril)methane Sulfenamide, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole, chloromethyl-n-octyldisulfide and the like can also be used.

As the antifouling agent (C), each of the compounds exemplified above can be used alone or in combination of two or more. In addition, among the compounds exemplified above, as the antifouling agent (C), from the viewpoint of exhibiting stable antifouling performance, it is preferable to use cuprous oxide, and in particular, it is preferable to use cuprous oxide and copper pyrithione in combination. .

[Anti-fouling paint composition and painted products]

The antifouling paint composition of the present invention is an antifouling paint composition comprising the polyester resin (A), the silylester group-containing resin (B) and the antifouling agent (C), wherein the polyester resin (A) and The mass ratio of the silyl ester group-containing resin (B) is in the range of 3/97 to 80/20, and the content of the antifouling agent (C) is between the polyester resin (A) and the silyl ester group-containing resin (B). It is characterized in that it is within the range of 50 to 500 mass% based on the total mass of).

The mass ratio of the polyester resin (A) and the silyl ester group-containing resin (B) is within the range of 3/97 to 80/20, preferably within the range of 7/93 to 60/40, more preferably It is within the range of 10/90 to 40/60. When the mass ratio of the polyester resin (A) and the resin (B) containing a silicester group is within the range of 3/97 to 80/20, the antifouling performance of the antifouling coating film obtained by the antifouling coating composition of the present invention is excellent. can be maintained over a long period of time, and it is difficult to cause film defects such as film peeling, blisters, and cracks in the antifouling film. When the mass ratio of the polyester resin (A) and the silyl ester group-containing resin (B) is less than 3/97 or greater than 80/20, it becomes difficult to maintain the antifouling performance of the obtained coating film for a long period of time. there is

The content of the antifouling agent (C) is in the range of 50 to 500 mass% based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B), preferably 250 to 400 It is within the range of 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, and if the content of the antifouling agent (C) is greater than 500% by mass, The physical properties of the obtained coating film may deteriorate, causing defects such as peeling and swelling.

The antifouling coating composition of the present invention, in addition to the above polyester resin (A), silyl ester group-containing resin (B) and antifouling agent (C), pigments, dyes, dehydrating agents, plasticizers, thixotropic agents (flow inhibitors), antifoaming agents, antioxidants, resins other than the polyester resin (A) or the silylester group-containing resin (B), organic acids, solvents, and the like, various components used in general paint compositions can be blended as necessary. . These components can be used individually or in combination of 2 or more types.

As the pigment, for example, coloring pigments such as bengala, talc, titanium oxide, yellow iron oxide, silica, calcium carbonate, barium sulfate, calcium oxide, carbon black, naphthol red, phthalocyanine blue, talc, silica, mica, clay, carbonic acid and extender pigments such as calcium, 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, and 1 to 500% by mass based on the total mass of the polyester resin (A) and the silylester group-containing resin (B). It is more preferable that it is within the range of.

The dehydrating agent is a component that contributes to improving the storage stability of the paint. Examples of such a dehydrating agent include anhydrous gypsum, hemihydrate gypsum (calcined gypsum), synthetic zeolite-based adsorbents (trade name 'Molecular Sieve', etc.) methyl formate, methyl orthoacetate, orthoboric acid ester, etc.), silicates, isocyanates, and the like can also be used. Among these, anhydrous gypsum and hemihydrate gypsum (calcined gypsum), which are inorganic dehydrating agents, are preferable. In addition, these dehydrating agents may be used independently or may use 2 or more types together. On the other hand, the content of the dehydrating agent in the antifouling coating composition can be appropriately adjusted, but it is within the range of 0 to 100 mass% based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B). It is preferable, and it is more preferable that it exists in the range of 0.5-25 mass %.

The above plasticizer is a component that contributes to improvement of crack resistance and water resistance of the antifouling coating film obtained. 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, and the like. can be heard These plasticizers may be used independently or may use 2 or more types together. The content of the plasticizer in the antifouling coating composition can be appropriately adjusted, but is preferably in the range of 0.5 to 10 mass% based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B), It is more preferable that it exists in the range of 1-5 mass %.

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

Examples of the thixotropic agent include organic waxes (polyethylene wax, polyethylene oxide wax, polyamide wax, amide wax, hydrogenated castor oil wax, etc.), organic clay compounds (amine salts of Al, Ca, Zn, stearate salts, lecithin salts, alkyl sulfonic acid salts, etc.), bentonite, synthetic fine powder silica, and the like. These thixotropic agents may be used alone or in combination of two or more. The content of the thixotropic agent in the antifouling coating composition can be appropriately adjusted, for example, within the range of 0.25 to 50 mass% based on the total mass of the polyester resin (A) and the silyl ester group-containing resin (B). to be.

In addition to the polyester resin (A) and the silylester group-containing resin (B) as described above, the antifouling coating composition of the present invention may contain one or two or more other resins as necessary, and those Examples of such resins include acrylic resins, acrylic silicone resins, epoxy resins, fluorine resins, polybutene resins, silicone rubbers, urethane resins, polyamide resins, vinyl chloride copolymer resins, chlorinated rubbers, which do not have a silyl ester group, and chlorinated olefin resins, styrene-butadiene copolymer resins, ketone resins, ethylene-vinyl acetate copolymer resins, vinyl chloride resins, alkyd resins, camarone resins, terpene phenol resins, and petroleum resins.

In addition, the antifouling coating composition of the present invention may contain a known rosin-based compound. Examples of such a rosin-based compound include rosin, rosin derivatives, and rosin metal salts. Examples of the rosin include tologin, gum rosin, and wood rosin. Examples of the rosin derivative include hydrogenated rosin, maleinized rosin obtained by reacting rosin with maleic anhydride, formylated rosin, and polymerized rosin. Examples of the metal salt of rosin include zinc loginate, calcium loginate, caparojinate, magnesium loginate, and other metal compounds and reaction products of rosin. These rosin-type compounds can be used individually or in combination of 2 or more types.

The amount of the rosin-based compound 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 silylester group-containing resin (B). desirable.

The antifouling paint composition of the present invention is 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 ether, propylene glycol mono Organic solvents commonly used as solvents for antifouling paints such as methyl ether acetate, etc.) and alcohol solvents (isopropyl alcohol, etc.) can be blended. On the other hand, the blending amount of the organic solvent can be appropriately adjusted. For example, the blending amount is such that the total solid content of the antifouling coating composition is in the range of 20 to 90% by mass, and may be further added depending on workability at the time of coating.

The antifouling coating composition of the present invention can be prepared by the same method as the known antifouling coating composition. For example, by adding the polyester resin (A), the silyl ester group-containing resin (B), the antifouling agent (C), and, if necessary, the above-mentioned organic solvents and additives, etc. to a stirring tank at once or sequentially, stirring, and mixing. can be manufactured

The coated article of the present invention is an article obtained by coating the surface of a substrate with the antifouling paint composition of the present invention. The coated article is produced by a manufacturing method comprising the steps of applying or impregnating the antifouling coating composition on at least the surface of a substrate once or several times, and drying the antifouling coating composition coating the surface of the substrate. You can get it.

As the substrate, for example, a substrate in contact with seawater or fresh water (eg, constantly or intermittently), specifically an underwater structure; outer shell or bottom; aqueducts or cooling pipes in power plants; Fishing nets, fishing gear, or floats used for aquaculture or stationary purposes; Fishing net accessories, such as a rope, etc. are mentioned. 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, etc., for example, 30 to 250 μm / times, preferably about 75 to 150 μm/time, and if necessary, two or more overlapping applications may be applied.

The antifouling paint composition of the present invention may be coated on the surface of the base material after applying plasma, antifouling paint, and, if necessary, a binder paint, by means such as brush application, spray application, roller application, or dipping. . In addition, the antifouling coating composition of the present invention may be coated over the surface of an existing antifouling coating film. Drying of the coating film can be performed at room temperature, but heat drying may be performed at a temperature of up to about 100°C if necessary.

Example

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited only to Examples. Meanwhile, 'parts' and '%' in the following examples mean 'parts by mass' and '% by mass', respectively.

Preparation 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 put into a 2L reactor equipped with a thermometer, stirrer and rectification column, and the temperature of the contents of the reactor was raised to 160°C. Subsequently, the temperature was raised from 160 ° C to 230 ° C in 3 hours, and after maintaining the temperature of the contents at 230 ° C for 2 hours, the rectification column was replaced with a water reactor, and about 50.0 parts of xylene was added to the reactor, and water and xylene were mixed. Polycondensation was performed while boiling together to remove condensation water. After confirming that the produced polyester resin had an acid value of 1.0 mgKOH/g or less, heating was stopped, cooling was started, and xylene was added and diluted to obtain a polyester resin (A1) solution having a solid content of 70%. On the other hand, the resin acid value was measured by dissolving a measurement sample using a mixed solution of toluene and isopropanol (mass ratio: 1/1) as a solvent and titrating an alcohol-based solution of 1/10 normal potassium hydroxide.

Here, the relationship between the abbreviation of the polyester raw material in this 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; neopentylglycol, 1,6-HD; 1,6-hexanediol, BEPG; 2-butyl-2-ethyl-1,3-propanediol, CHDM; 1,4-cyclohexanedimethanol, DEG; diethylene glycol, TEG; triethylene glycol, tetraEG; tetraethylene glycol, DPG; dipropylene glycol, TMP; trimethylolpropane, G; glycerin, PE; pentaerythritol

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

Each polyester resin having a solid content of 70% (A2) to (A12), (A16), and (A17) A resin solution was obtained. On the other hand, in Production Example 17, since it was difficult to reduce the acid value of the polyester resin to be produced to 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 placed in a 2L reactor equipped with a thermometer, stirrer and rectification column, and the temperature of the contents of the reactor was raised to 160°C. Subsequently, the temperature was raised from 160 ° C to 230 ° C in 3 hours, and after maintaining the temperature of the contents at 230 ° C for 2 hours, the rectification column was replaced with a water reactor, and about 50.0 parts of xylene was added to the reactor, and water and xylene were mixed. Polycondensation was performed while boiling together to remove condensation water. After confirming that the produced polyester resin had an acid value of 1.0 mgKOH/g or less, the temperature of the contents was cooled to 160°C. Further, 112.3 parts of PA was added, held at 160 DEG C for 1 hour to carry out an addition reaction (half esterification), and then cooling was started. After cooling to 130°C, a resin solution of a polyester resin (A13) having a solid content of 70% was obtained by adding and diluting with xylene.

(Production Example 14) Production of polyester resin (A14)

A resin solution of a 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 alcohol component in Production Example 13 were formulated 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 acids, and 50.0 parts of xylene were put into a 2L reactor equipped with a thermometer, stirrer and water separator, and the temperature of the contents of the reactor was 160 ° C. The temperature was raised to and maintained for 1 hour. Subsequently, the temperature was raised from 160 ° C. to 240 ° C. in 4 hours, and polycondensation proceeded while removing the generated condensation water in the state of 240 ° C. After confirming that the resin acid value was about 3.0 mgKOH/g or less, heating was stopped, 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 values and weight average molecular weights of the polyester resins (A1) to (A17) obtained in each of the above production examples are shown in Table 1 together with the compounding amounts of each production example.

[Table 1]

Silyl ester group Preparation of oleoresin (B)

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

After adding 40 parts of xylene to a flask equipped with an agitator, the liquidus temperature was maintained at 140° C., and each monomer of each unsaturated monomer listed in Table 2 and the peroxide polymerization initiator “Perbutyl I” (trade name, Nichiyu ( Note) The mixture with product) 1 part was dropped into Frasco for 3 hours. After completion, it was maintained at the same temperature for 30 minutes. Subsequently, a mixture of 10 parts of xylene and 1 part of 'Perbutyl I' was dropped for 20 minutes, and after stirring was continued at the same temperature for 2 hours, cooling of the liquid phase was started. A resin solution was prepared by adding xylene to plastic so that the solid content concentration of the resulting resin was 50% by mass, thereby obtaining a resin solution of a silyl ester group-containing resin (B1).

(Production Examples 19 and 20) Production of silyl ester group-containing resins (B2) and (B3)

A resin solution of silyl ester group-containing resins (B2) and (B3) (solid content concentration: 50% by mass) was obtained in the same manner as in Production Example 18, except that the unsaturated monomers in Production Example 18 were formulated as shown in Table 2. .

[Table 2]

Preparation of antifouling paint composition and various tests

(Examples 1 to 23) and (Comparative Examples 1 to 5)

evaluation

Resin solutions of polyester resins (A1) to (A17), resin solutions of silicester group-containing resins (B1) to (B3), antifouling agents, pigments, etc. are mixed in the formulations shown in Tables 3-1 and 3-2. and mixed and dispersed using a homomixer at a stirring speed of about 2,000 rpm. After dispersion, Disparon A630-20XN (manufactured by Kusumoto Chemical Co., Ltd., anti-flow agent) and a solvent were added, followed by disper stirring to prepare paint compositions (E1) to (E28). The prepared coating composition was subjected to the following antifouling performance test, adhesion test and crack resistance test. The results of each of these tests are shown in Tables 4 to 6.

<Contamination prevention performance test>

On both sides of a sandblasted steel sheet (100 mm × 300 mm × 2 mm), an epoxy-based rust-preventive paint was spray-coated to a dry film thickness of 200 μm, and an epoxy-based binder coat was further coated to a dry film thickness of 100 μm. . On both sides of the painted board, each of the above paint compositions was coated four times by spray coating so that the dry film thickness on one side was 480 μm, and dried for 1 week in a constant temperature and humidity room at a temperature of 20 ° C and a humidity of 75% to obtain a test piece. produced. Using this test piece, it was immersed in seawater for 48 months in Owase Bay, Mieken, and the ratio (adhesion area) of the area occupied by adherent organisms on the test film was measured over time.

◎: (Pass) no attached organisms were observed

○: (Pass) Area occupied by attached organisms is less than 5%

△: (Disqualified) Area occupied by attached organisms is 5% or more and less than 30%

×: (Disqualified) Area occupied by attached organisms is 30% or more

<Adhesion test>

To a sandblasted steel sheet (120 mm x 120 mm x 1 mm) having a curvature that can be mounted on a cylindrical drum (diameter 500 mm x height 240 mm), an epoxy-based anti-rust paint is spray-coated to a dry film thickness of 200 µm, and further epoxy is applied. The based binder coat was applied to a dry film thickness of 100 µm. On one side of the steel sheet after this coating, each of the above coating compositions was coated 4 times by spray coating so that the dry film thickness on one side was 480 μm, and dried for 1 week in a constant temperature and humidity room at 20 ° C and 75% humidity, and the test piece was produced. This test piece was mounted on the above cylindrical drum, and the cylindrical drum was rotated at 16 knots at 500 mm below sea level in Yura Bay, Hyogo Prefecture for 24 months. The test pieces were recovered over time from the sea, and a grid test was conducted at 5 mm intervals. Evaluation was based on ISO 2409:1992.

◎: (Pass) Table1 Classification 0 1

○: (Pass) Table1 Classification 2

△: (disqualified) Table 1 Classification 3

×: (disqualified) Table 1 Classification 4 5

<Crack resistance test>

The coating film of the test piece subjected to the above adhesion test was visually observed, and the presence or absence of cracks was investigated.

◎: (pass) cracks were not observed

○: (Pass) Fine cracks are observed in a range of a part of the surface of the coating film

△: (Rejected) Fine or clear cracks are observed over a wide range of the surface of the coating film

×: (disqualified) Cracks reaching the bottom were observed

[Table 3-1]

[Table 3-2]

[Table 4]

[Table 5]

[Table 6]

Claims (6)

An antifouling paint composition comprising a polyester resin (A), a silyl ester group-containing resin (B) and an antifouling agent (C),
The silyl ester group-containing resin (B) has the general formula (I):

[In formula (I), R ⁴ represents a hydrogen atom or a methyl group, R ¹ , R ² and R ³ each independently represents a hydrocarbon group, and the hydrocarbon group is a linear or branched alkyl group having 1 to 10 carbon atoms , Or a substituted or unsubstituted phenyl group by any substituent, R ⁵ is a hydrogen atom or R ⁶ -O-CO- (provided that R ⁶ is an organic group or a silyl group represented by -SiR ⁷ R ⁸ R ⁹ , The organic group is a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an unsaturated alkyl group or an aralkyl group, R ⁷ , R ⁸ and R ⁹ each independently represent a hydrocarbon group, and the hydrocarbon group has 1 to 10 carbon atoms. represents a 10-membered linear or branched alkyl group, or a phenyl group substituted or unsubstituted by an arbitrary substituent)], and one or two or more kinds of monomers (b1) represented by, other than the above monomers (b1) It consists of a copolymer with one or two or more of the monomers (b2) of, and the monomers (b2) are (meth)acrylic acid alkyl, (meth)acrylic acid alkoxyalkyl; (meth)acrylic acid alkylene glycol monomethyl, (meth)acrylic acid hydroxyalkyl of hydroxyl group-containing monomers, nitrogen-containing monomers, (meth)acrylic acid esters, vinyl chloride, vinylidene chloride, (meth)acrylonitrile, vinyl acetate, butyl vinyl ether, lauryl vinyl ether, N-vinylpyrrolidone, styrene, vinyltoluene, α-methylstyrene, a carboxyl group-containing monomer, an epoxy group-containing monomer, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, or a carbonyl group-containing monomer,
The mass ratio of the polyester resin (A) to the silyl ester group-containing resin (B) is in the range of 10/90 to 40/60, and the acid value of the polyester resin (A) is in the range of 0 to 45 mgKOH/g. And, the weight average molecular weight of the polyester resin (A) is in the range of 500 to 4,000, and the content of the antifouling agent (C) is the relationship between the polyester resin (A) and the silyl ester group-containing resin (B). The antifouling paint composition, characterized in that in the range of 50 to 500% by mass based on the total mass. delete delete delete According to claim 1,
The silyl ester group-containing resin (B) has a mass ratio (b1) / (b2) of the monomer (b1) and the monomer (b2) in the range of 20/80 to 70/30. A coated article obtained by applying the antifouling coating composition according to claim 1 or 5 to an object to be coated.