CN106905802B

CN106905802B - Antifouling coating composition and coated article having coating film thereof

Info

Publication number: CN106905802B
Application number: CN201610945373.5A
Authority: CN
Inventors: 川村力; 梅田穰; 北岛昌和
Original assignee: Kansai Paint Co Ltd; NKM Coatings Co Ltd
Current assignee: Kansai Paint Co Ltd; Kansai Paint Marine Co Ltd
Priority date: 2015-10-27
Filing date: 2016-10-26
Publication date: 2021-06-25
Anticipated expiration: 2036-10-26
Also published as: CN106905802A; KR20170049392A

Abstract

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 can form an antifouling coating film that is less likely to cause coating film defects such as peeling, bubbling, and cracking of the coating film, and a coated article such as a fishing net, a ship, a marine structure, or a harbor coastal structure having a coating film of the antifouling coating composition. The present invention relates to an antifouling paint composition comprising a polyester resin having a specific constituent unit in the resin skeleton, a silyl ester group-containing resin and/or a resin having a metal carboxylate structure, and an antifouling agent, and a coated article having a coating film of the composition.

Description

Antifouling coating composition and coated article having coating film thereof

Technical Field

The present invention relates to an antifouling paint composition and a coated article having a coating film thereof, and more particularly, to an antifouling paint composition capable of forming an antifouling coating film capable of maintaining excellent antifouling properties over a long period of time, and a coated article having a coating film thereof.

Background

In recent years, as a resin for an antifouling paint which replaces an organotin-containing copolymer which is concerned about marine pollution, various studies have been made on a resin having hydrolyzability in seawater. When a coating film formed on the surface of a structure such as a ship, which is in contact with seawater, is brought into contact with seawater using an antifouling paint composition containing such a resin having hydrolyzability (i.e., a hydrolysis-type antifouling paint composition), the resin having hydrolyzability can be gradually hydrolyzed to gradually dissolve the coating film in seawater, and the surface of the coating film is continuously renewed, thereby making it possible to maintain the antifouling performance. As a resin having hydrolyzability in seawater, many hydrolysis type antifouling paint compositions containing a resin containing a trialkylsilyl ester group or a resin having a metal carboxylate structure have been proposed so far. However, the trialkylsilyl ester group-containing resins have different hydrolysis rates depending on the type of the alkyl group of the trialkylsilyl ester group or the structure of the resin, and the resins having a metal carboxylate structure have different hydrolysis rates depending on the type of the metal or the structure of the resin, and therefore, it is difficult to control the dissolution rate of a coating film obtained in many antifouling coating compositions using these hydrolyzable resins in seawater.

Therefore, a method of controlling the dissolution rate of a coating film by using a combination of a hydrolyzable resin and rosin or a rosin derivative of the above type (see patent documents 1 to 6) has been studied. By using a resin having hydrolyzability in combination with rosin or a rosin derivative in this way, the dissolution rate of the coating film can be controlled to some extent, but when the amount of rosin or a rosin derivative used is small, the solubility of the coating film in seawater cannot be sufficiently obtained, and it is difficult to maintain the antifouling performance of the coating film. On the other hand, when the amount of rosin or rosin derivative used is large, the dissolution rate of the coating film into seawater increases to improve the antifouling performance, but the physical properties and adhesiveness of the coating film decrease, so that coating film defects such as peeling, bubbling, and cracking of the coating film are likely to occur, and it is difficult to maintain the antifouling performance for a long period of time.

In order to solve these problems, an antifouling paint composition containing a polyester resin and a trialkylsilyl ester group-containing resin at a mass ratio within a specific range has been proposed (see patent document 7). According to the antifouling paint composition, although an antifouling coating film having excellent antifouling property and being less likely to cause coating film defects such as bubbling and cracking can be formed, further improvement is being sought because the coating film performance is sometimes slightly insufficient in terms of maintaining the antifouling performance for a long period of time depending on the sea area to which the antifouling coating film is exposed or the paint composition.

Documents of the prior art

Patent document

Patent document 1: japanese unexamined patent publication Hei 10-30071

Patent document 2: japanese laid-open patent publication No. 2002-53797

Patent document 3: japanese patent laid-open publication No. 2011-26357

Patent document 4: japanese laid-open patent publication No. 2011-32489

Patent document 5: international publication No. 2011/046087

Patent document 6: japanese unexamined patent publication Hei 9-286933

Patent document 7: international publication No. 2015/156073

Disclosure of Invention

Problems to be solved by the invention

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 can form an antifouling coating film that is less likely to cause coating film defects such as peeling, bubbling, and cracking of the coating film, and a coated article such as a fishing net, a ship, a marine structure, or a harbor coastal structure having a coating film of the antifouling coating composition.

Means for solving the problems

The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a coating film obtained from an antifouling coating composition comprising a polyester resin (a) having a specific constituent unit in the resin skeleton, a silyl ester group-containing resin (B1) and/or a resin having a metal carboxylate structure (B2), and an antifouling agent (C) can control the dissolution rate of the coating film in the sea, can maintain excellent antifouling properties over a long period of time, and has excellent physical properties of the coating film, and therefore, when the antifouling coating composition is applied to the bottom of a ship, coating film defects such as peeling, bubbling, and cracking of the coating film are less likely to occur during voyage or berthing. The present invention has been completed based on such findings.

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

(item 1) an antifouling paint composition comprising a polyester resin (A), a silyl ester group-containing resin (B1) and/or a resin having a metal carboxylate structure (B2), and an antifouling agent (C), wherein the polyester resin (A) has a constituent unit represented by the following formula (1) in the resin skeleton, the total mass of the constituent units is in the range of 2 to 50 mass% based on the mass of the polyester resin (A), and the total mass ratio of the polyester resin (A), the silyl ester group-containing resin (B1), and the resin having a metal carboxylate structure (B2) is in the range of 3/97 to 80/20.

[ CHEM 1 ]

(in the formula, R₀Represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 100. )

(item 2) the antifouling paint composition according to item 1, wherein the silyl ester group-containing resin (B1) is a copolymer of 1 or 2 or more kinds of the monomer (B1) represented by the following formula (2) and 1 or 2 or more kinds of the monomer (B2) other than the monomer (B1).

[ CHEM 2 ]

[ in the formula, R₄Represents a hydrogen atom or a methyl group, R₁、R₂And R₃Each independently represents a hydrocarbon group, R₅Represents a hydrogen atom or R₆-O-CO- (wherein, R₆Represents an organic group or-SiR₇R₈R₉Silyl radical of formula R₇、R₈And R₉Each independently represents a hydrocarbon group. ).]

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

[ CHEM 3 ]

(wherein M represents a 2-valent metal atom, and X represents at least 1 group selected from the group consisting of a hydroxyl group, an organic acid residue, and an alcohol residue.)

(item 4) the antifouling paint composition according to any one of items 1 to 3, wherein the polyester resin (A) is produced using at least one raw material mixture comprising at least 1 component selected from the group consisting of lactic acid, lactide of lactic acid, and polylactic acid, and at least 1 component selected from the group consisting of glycolic acid, glycolide, and polyglycolic acid, and has an acid value in the range of 0.1 to 120 KOHmg/g.

(item 5) the antifouling paint composition as claimed in any of items 1 to 4, wherein the polyester resin (A) has a weight average molecular weight in the range of 190 to 15000.

(item 6) the antifouling paint composition as claimed in any of items 1 to 5, wherein the polyester resin (A) is a polyester resin having no metal carboxylate structure.

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

ADVANTAGEOUS EFFECTS OF INVENTION

The antifouling paint composition of the present invention can maintain excellent antifouling property over a long period of time, and can form a coating film in which coating film defects such as peeling, bubbling, and cracking of the coating film are not easily generated.

Detailed Description

The antifouling paint composition comprises a polyester resin (A), a silyl ester group-containing resin (B1) and/or a resin (B2) having a metal carboxylate structure, and an antifouling agent (C), wherein the polyester resin (A) has a constituent unit represented by the following formula (1) in the resin skeleton, the total mass of the constituent units is in the range of 2 to 50 mass% based on the mass of the polyester resin (A), and the total mass ratio of the polyester resin (A), the silyl ester group-containing resin (B1), and the resin (B2) having a metal carboxylate structure is in the range of 3/97 to 80/20.

[ CHEM 4 ]

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

[ polyester resin (A) ]

The polyester resin (A) used in the antifouling paint composition of the invention has a constituent unit represented by the formula (1) in the resin skeleton. In order to introduce the constituent unit represented by the formula (1) into the polyester resin, it is preferable to use, as a raw material, at least 1 component selected from the group consisting of lactic acid, lactide of lactic acid, and polylactic acid, and at least one component selected from at least 1 component selected from the group consisting of glycolic acid, glycolide, and polyglycolic acid in the production of the resin. Incidentally, glycolide is also referred to as 1,4-di in the present specification

Alkane-2, 5-dione (1,4-Dioxane-2, 5-dione).

In addition, the total mass of the constituent units represented by the formula (1) is R in the formula (1)₀In the case of methyl, R in the formula (1) is in the range of 2 to 50 mass%, preferably 5 to 40 mass%, and more preferably 10 to 30 mass% based on the mass of the polyester resin (A)₀In the case of a hydrogen atom, the amount is in the range of 2 to 50 mass%, preferably 4 to 40 mass%, and more preferably 6 to 30 mass% based on the mass of the polyester resin (A). In the constitution sheetWhen the total mass of the elements is less than 2% by mass or more than 50% by mass, it may be difficult to maintain the antifouling property of the obtained coating film for a long period of time.

The polyester resin (a) can be produced by a conventionally known method, and at least one component selected from the group consisting of at least 1 component selected from the group consisting of lactic acid, lactide of lactic acid, and polylactic acid, and at least 1 component selected from the group consisting of glycolic acid, glycolide, and polyglycolic acid; lactic acid, lactide of lactic acid, polylactic acid, glycolic acid, glycolide, and an acid component other than polyglycolic acid (a 1); and lactic acid, lactide of lactic acid, polylactic acid, and an alcohol component (a2) other than glycolic acid, glycolide, and polyglycolic acid, and these components are reacted with each other.

The above reaction for producing the polyester resin (a) includes any of known reactions such as an esterification reaction, a transesterification reaction, a ring-opening polymerization reaction, and a ring-opening addition reaction. In the present specification, the reaction for producing the polyester resin (a) may be referred to as a "polymerization reaction".

Lactic acid, lactide of lactic acid and polylactic acid

In the production of the polyester resin (a), lactic acid, lactide of lactic acid, and polylactic acid may be used as they are. These compounds each have an optical isomer, but in the present invention, a compound containing an L-form and a D-form at an arbitrary ratio can be used. In order to form an antifouling coating film which can maintain excellent antifouling properties over a long period of time and is less likely to cause coating film defects such as peeling, blistering, and cracking, lactide of lactic acid and/or polylactic acid is particularly preferably used among the above compounds in the production of the polyester resin (a).

Glycolic acid, glycolide and polyglycolic acid

In the production of the polyester resin (a), glycolic acid, glycolide, and polyglycolic acid may be used as they are as commercially available products. Among the above compounds, glycolic acid and/or glycolide is particularly preferably used in the production of the polyester resin (a) in order to form an antifouling coating film which can maintain excellent antifouling properties over a long period of time and is less likely to cause coating film defects such as peeling, bubbling, and cracking of the coating film.

In the production of the polyester resin (a), polylactic acid and polyglycolic acid each having a weight average molecular weight of 450 to 1000000 may be used.

Acid component (a1)

In the present invention, as the acid component (a1), an acid component generally used for the production of polyester resins can be used. Examples of such an acid component include: alicyclic polybasic acids, aliphatic polybasic acids, aromatic monocarboxylic acids, aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and esters, anhydrides, and halides of these acids.

The alicyclic polybasic acid is generally a compound having 1 or more alicyclic structures (mainly 4 to 6-membered rings) and 2 or more carboxyl groups in 1 molecule, and an acid anhydride, an ester, a halide, and the like of the compound. Examples of the alicyclic polybasic acid include: alicyclic polycarboxylic acids such as 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-dicarboxylic acid, tetramethylisophthalic acid, 3-methyl-1, 2-cyclohexanedicarboxylic acid, 4-methyl-1, 2-cyclohexanedicarboxylic acid, 1,2, 4-cyclohexanetricarboxylic acid, and 1,3, 5-cyclohexanetricarboxylic acid; anhydrides of these alicyclic polycarboxylic acids; lower alkyl esters of these alicyclic polycarboxylic acids, and the like, and these may be used alone or in combination of 2 or more.

The aliphatic polybasic acid is generally an aliphatic compound having 2 or more carboxyl groups in 1 molecule, an acid anhydride of the aliphatic compound, or a halide of the aliphatic compound. Examples of the aliphatic polybasic acid include: aliphatic polycarboxylic acids such as succinic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, octadecanedioic acid, and citric acid; anhydrides of these aliphatic polycarboxylic acids; halides of these aliphatic polycarboxylic acids, and the like, and these may be used alone or in combination of 2 or more.

The aromatic polybasic acid is generally an aromatic compound having 2 or more carboxyl groups in 1 molecule, and an acid anhydride, an ester or a halide of the aromatic compound.

Examples of the aromatic polybasic acid having 2 carboxyl groups in 1 molecule include: aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and 4, 4' -biphenyldicarboxylic acid; anhydrides of these aromatic polycarboxylic acids, and the like.

Examples of the aromatic polybasic acid having 3 or more carboxyl groups in 1 molecule include a 3-membered aromatic polybasic carboxylic acid, a 4-membered aromatic polybasic carboxylic acid, and the like. Examples of the 3-membered aromatic polycarboxylic acid include: trimellitic acids such as trimellitic acid, trimellitic anhydride, trimellitic acid alkyl ester, and trimellitic acid halide; trimellitic acids such as trimellitic acid, trimellitic anhydride, trimellitic acid alkyl ester, and trimellitic acid halide; trimesic acids such as trimesic acid, alkyl trimesates, and trimesic acid halides; various naphthalene tricarboxylic acids and anhydrides thereof having different bonding positions of carboxyl groups to aromatic rings; various anthracene tricarboxylic acids and anhydrides thereof with different bonding positions of carboxyl groups to aromatic rings; various biphenyl tricarboxylic acids and anhydrides thereof having different bonding positions of carboxyl groups to aromatic rings; various benzophenone tricarboxylic acids and anhydrides thereof having different bonding positions of carboxyl groups to aromatic rings; ethylene bis trimellitic acid and its anhydride, and the like. Examples of the 4-membered aromatic polycarboxylic acid include: pyromellitic acids such as pyromellitic acid, pyromellitic dianhydride, pyromellitic acid alkyl ester, and pyromellitic acid halide; trimellitic acids such as trimellitic acid, trimellitic dianhydride, trimellitic acid alkyl esters, and trimellitic acid halides; and pyromellitic acids such as pyromellitic acid (rhetic acid), pyromellitic anhydride, alkyl pyromellitate, and halide of pyromellitic acid. The aromatic polybasic acids may be used singly or in combination of 2 or more.

In the present invention, as the acid component (a1) used for producing the polyester resin (a), a monocarboxylic acid such as an aromatic monocarboxylic acid, an aliphatic monocarboxylic acid, or an alicyclic monocarboxylic acid can be used. Examples of the aromatic monocarboxylic acid include: benzoic acid, methylbenzoic acid, ethylbenzoic acid, p-tert-butylbenzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, and the like. Examples of the aliphatic monocarboxylic acid include: acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tetradecanoic acid, palmitic acid, stearic acid, oleic acid, elaidic acid, brassidic acid, linoleic acid, linolenic acid, rosin acid, coconut oil fatty acid, cottonseed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil 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, safflower oil fatty acid and other saturated or unsaturated aliphatic monocarboxylic acids, and these may be used alone or in combination of 2 or more.

Examples of the alicyclic monocarboxylic acid include: cyclohexane carboxylic acid, cyclopentane carboxylic acid, cycloheptane carboxylic acid, 4-ethyl cyclohexane carboxylic acid, 4-hexyl cyclohexane carboxylic acid, 4-lauryl cyclohexane carboxylic acid, these can be used alone or in combination of 2 or more.

In the present invention, the acid component (a1) used for the production of the polyester resin (a) may contain an esterified product such as a glyceride of the above-mentioned monocarboxylic acid. Examples of the glycerol ester of monocarboxylic acid include: coconut oil, cottonseed oil, hemp seed oil, rice bran oil, fish oil, tall oil, soybean oil, linseed oil, tung oil, rapeseed oil, castor oil, dehydrated castor oil, safflower oil and the like.

In the present invention, the acid component (a1) used for the production of the polyester resin (a) preferably contains an aromatic polybasic acid in an amount of 30 mol% or more, preferably 50 mol% or more, and more preferably 70 mol% or more, based on the total mole number of the acid components (a1), from the viewpoint of maintaining the antifouling property for a long period of time.

Alcohol component (a2)

In the present invention, alcohol components generally used for the production of polyester resins can be used as the alcohol component (a 2). Such an alcohol component is preferably a component containing a 2-membered alcohol and/or a 3-membered or higher polyol such as an alicyclic diol, an aliphatic diol, and an aromatic diol, and examples thereof include: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, 1, 2-propanediol, di-1, 2-propanediol, tri-1, 2-propanediol, 1, 2-butanediol, 2, 3-butanediol, 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-diethyl-1, 3-propanediol, 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-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, tricyclodecanedimethanol, 2-dimethyl-3-hydroxypropyl-2, 2-dimethyl-3-hydroxypropionate (esterified product of hydroxypivalic acid and neopentyl glycol), bisphenol A, bisphenol F, an oxyalkylene adduct of bisphenol A, bis (4-hydroxyhexyl) -2, 2-propane, bis (4-hydroxyhexyl) methane, an ester diol compound such as 3, 9-bis (1, 1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5,5] undecane or bis (hydroxyethyl) terephthalate, glycerol, diglycerol, triglycerol, 1,2, 6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolethane, trimethylolpropane, ditrimethylolpropane or tris (2-hydroxyethyl) isocyanurate, and a polylactone polylol obtained by adding a lactone compound such as epsilon-caprolactone to these polyols Compounds and the like, which may be used alone or in combination of 2 or more.

Further, if necessary, a monoalcohol such as methanol, ethanol, propanol, n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, stearyl alcohol, 2-phenoxyethanol, lauryl alcohol, etc.; an alcohol compound obtained by reacting a monoepoxy compound such as ethylene oxide, propylene oxide, butylene oxide, or a glycidyl ester of a synthetic highly branched saturated fatty acid (trade name "Cardura E10," manufactured by HEXION Specialty Chemicals ") with a compound having a protonic acid is used as a side 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 the production can be carried out by a known method. The polyester resin (a) can be produced by, for example, subjecting at least 1 component selected from the group consisting of lactic acid, lactide of lactic acid, and polylactic acid, and at least 1 component selected from the group consisting of glycolic acid, glycolide, and polyglycolic acid, 1 or 2 or more of the acid components (a1), and 1 or 2 or more of the alcohol components (a2) to a polymerization reaction in a nitrogen stream at a temperature of 150 to 250 ℃ for 2 to 10 hours. In the above polymerization reaction, the order of the reaction of the raw materials may be arbitrarily adjusted, and for example, after polylactic acid is obtained by subjecting lactide of lactic acid to a ring-opening polymerization reaction in advance, or after polyglycolic acid is obtained by subjecting glycolide to a ring-opening polymerization reaction in advance, the acid component (a1) and the alcohol component (a2) may be subjected to a polymerization reaction in the presence of the ring-opening polymer. The polyester resin (a) may be obtained by polymerization and/or transesterification of the polyester resin obtained by polymerization of the acid component (a1) and the alcohol component (a2) with lactide or glycolide of lactic acid. These reactions may be carried out in the presence of a known organic solvent.

In addition, the polymerization reaction may be carried out using a catalyst in order to promote the reaction. Examples of such catalysts include: known catalysts such as dibutyltin oxide, antimony trioxide, iron acetate, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, tetraisopropyl titanate, zinc borate, zinc chloride, zinc sulfate, zinc naphthenate, zinc oxide, lead borate, aluminum acetate, and aluminum chloride.

In the present invention, the polyester resin (a) is produced by a polymerization reaction of at least 1 component selected from lactic acid, lactide of lactic acid and polylactic acid, and at least 1 component selected from the group consisting of glycolic acid, glycolide and polyglycolic acid, the acid component (a1) and the alcohol component (a2), and may contain a known organic compound and/or inorganic compound other than the acid component (a1) and the alcohol component (a2) as a constituent component, and may be produced by a known chemical reaction accompanied by an amidation reaction, a urethanization reaction, an imidization reaction, a carbonation reaction, a urethanization reaction, or the like, as necessary. For example, the polyester resin (a) may be a modified polyester resin obtained by reacting a reaction intermediate or a reaction product with a metal compound such as organic acid zinc, organic acid copper, zinc chloride, copper chloride, zinc hydroxide, copper hydroxide, zinc oxide, or copper oxide, a fatty acid, an oil or fat, a mono-or polyisocyanate compound, a mono-or polyamine compound having nitrogen to which a hydrogen atom is bonded, an epoxy compound, an acrylic resin, a vinyl ester resin, or the like during or after a polymerization reaction. In the case where at least 1 component selected from the group consisting of glycolic acid, glycolide, and polyglycolic acid is used as a raw material for the polyester resin (a), an organic compound such as lactic acid, lactide of lactic acid, or polylactic acid may be contained as a constituent component other than the acid component (a1) and the alcohol component (a 2).

In this case, the content of the metal atom contained in the metal carboxylate structure based on the solid content mass of the polyester resin (a) is lower than the content of the metal atom contained in the resin (B2) having a metal carboxylate structure described later, preferably lower than 0.04 mol/kg, and more preferably the polyester resin (a) does not substantially have the metal carboxylate structure. When the polyester resin (a) has a metal carboxylate structure, the production cost of an antifouling paint composition using the resin may be increased.

In addition, when the antifouling paint composition of the present invention further contains a component containing a metal compound (for example, a pigment component, an antifouling agent component, or the like), the polyester resin (a) having substantially no metal carboxylate structure may react with the component containing the metal compound to form a metal carboxylate structure with time during production or storage of the antifouling paint composition. The content of the metal atom contained in the metal carboxylate structure thus formed is preferably in the range of less than 1.5 mol/kg, more preferably less than 0.04 mol/kg, based on the mass of the solid content of the polyester resin (a), from the viewpoint of storage stability of the antifouling paint composition.

The polyester resin (a) is preferably 80 mol% or more, more preferably 90 mol% or more of the total constituent components of the resin, and is derived from at least 1 component selected from the group consisting of lactic acid, lactide of lactic acid, and polylactic acid, and at least one component selected from at least 1 component selected from the group consisting of glycolic acid, glycolide, and polyglycolic acid, and the constituent components of the acid component (a1) and the alcohol component (a 2).

In addition, the resin acid value of the polyester resin (A) is preferably in the range of 0.1 to 120mgKOH/g, more preferably in the range of 0.1 to 95mgKOH/g, and particularly preferably in the range of 0.3 to 50mgKOH/g, from the viewpoint of maintaining the stain-proofing property of the resulting coating film over a long period of time.

Further, the weight average molecular weight of the polyester resin (A) is preferably in the range of 190 to 15000, more preferably in the range of 340 to 13000, and particularly preferably in the range of 600 to 8000, from the viewpoint of maintaining the antifouling property and the antifouling property of the resulting coating film over a long period of time.

In the present specification, the weight average molecular weight is a value obtained by converting a weight average molecular weight measured by gel permeation chromatography (available from Tosoh corporation, "HLC 8120 GPC") with reference to a weight average molecular weight of polystyrene. The weight average molecular weight was measured using 4 columns (trade names: "TSKgelG-4000 HxL", "TSKgelG-3000 HxL", "TSKgelG-2500 HxL" and "TSKgelG-2000 HxL" (all manufactured by Tosoh Co., Ltd.)) under conditions that the mobile phase was tetrahydrofuran, the measurement temperature was 40 ℃, the flow rate was 1 ml/min, and the detector was RI.

[ silyl ester group-containing resin (B1) ]

The antifouling paint composition of the present invention contains a silyl ester group-containing resin (B1) and/or a resin having a metal carboxylate structure (B2) in addition to the polyester resin (a). The silyl ester group-containing resin (B1) is a copolymer of 1 or 2 or more species of a monomer (B1) (hereinafter, sometimes referred to as "monomer (B1)") having a polymerizable unsaturated group and a triorganosilyl ester group represented by the following general formula (2) and 1 or 2 or more species of a monomer (B2) having a polymerizable unsaturated group other than the monomer (B1), preferably a copolymer having a weight average molecular weight (Mw) in the range of 1000 to 150000, and more preferably a copolymer having an Mw in the range of 3000 to 80000.

[ CHEM 5]

[ in the formula (2), R₄Represents a hydrogen atom or a methyl group, R₁、R₂And R₃Each independently represents a hydrocarbon group, R₅Represents a hydrogen atom or R₆-O-CO- (wherein, R₆Represents an organic group or-SiR₇R₈R₉Silyl radical of formula R₇、R₈And R₉Each independently represents a hydrocarbon group. ).]

When the Mw of the silyl ester group-containing resin (B1) used in the antifouling paint composition of the present invention is less than 1000, the dissolution rate of the coating film obtained from the antifouling paint composition increases, but the coating film has poor physical properties and is likely to have coating film defects such as blisters and cracks. When the Mw of the silyl ester group-containing resin (B1) exceeds 150000, the dissolution rate of a coating film obtained from the antifouling paint composition may be low, resulting in poor antifouling properties.

Further, R in the formula (2)₅In the case of a hydrogen atom, the monomer (b1) is represented by the following general formula (2-1).

[ CHEM 6 ]

R in the formula (2-1)₄、R₁、R₂And R₃Respectively with R in the formula (2)₄、R₁、R₂And R₃The same is true.

R in the formula (2) or the formula (2-1)₁、R₂And R₃The hydrocarbon group in (1) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or a phenyl group substituted or unsubstituted with an arbitrary substituent, and the hydrocarbon groups may be the same or different. Among them, the hydrocarbyl group is preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, or an isopropyl group.

Examples of the monomer represented by the above formula (2-1) (hereinafter referred to as "monomer (b 1-1)") include: trialkylsilyl (meth) acrylates such as trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, and triisopropylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate is preferred from the viewpoints of solubility of the obtained coating film, persistence of antifouling property, and difficulty in occurrence of bubbling and cracking.

R in the formula (2)₅Is "R₆-O-CO- "(wherein, R is₆Represents an organic group or-SiR₇R₈R₉Silyl radical of formula R₇、R₈And R₉Each independently represents a hydrocarbon group), the monomer (b1) is represented by the following general formula (2-2).

[ CHEM 7 ]

R in the formula (2-2)₄、R₁、R₂And R₃Respectively with R in the formula (2)₄、R₁、R₂And R₃The same is true.

As R in the formula (2) or the formula (2-2)₆Examples of the organic group include a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an unsaturated alkyl group, and an aralkyl group.

Examples of the above-mentioned linear or branched alkyl group having 1 to 10 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, 2-methylbutyl, 2-ethylbutyl, pentyl, 3-methylpentyl, hexyl, heptyl, octyl and the like.

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

Further, examples of the unsaturated alkyl group include: 2-propenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl and the like.

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

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

Examples of the monomer represented by the above formula (2-2) (hereinafter referred to as "monomer (b 1-2)") include: a maleic acid diester compound, a fumaric acid diester compound (R in the formula (2-2))₄A compound which is a hydrogen atom), and the like.

The formula (2) or R in the formula (2-2)₇、R₈And R₉The hydrocarbon group in (1) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or a phenyl group substituted or unsubstituted with an arbitrary substituent, and the hydrocarbon groups may be the same or different. Among these, the hydrocarbyl group is preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, or an isopropyl group.

The monomer (b1) is preferably an isopropylsilyl group-containing unsaturated monomer, in view of solubility of the resulting coating film, durability of antifouling property, and difficulty in occurrence of blisters or cracks. Examples of such isopropylsilyl group-containing unsaturated monomers include: triisopropylsilyl (meth) acrylate, triisopropylsilyl 4-pentenoate, bis (triisopropylsilyl) maleate, methyltriisopropylsilyl maleate, ethyltriisopropylsilyl maleate, n-butyltriisopropylsilyl maleate, isobutyltriisopropylsilyl maleate, tert-butyltriisopropylsilyl maleate, n-pentyltriisopropylsilyl maleate, isoamyltriisopropylsilyl maleate, 2-ethylhexyltriisopropylsilyl maleate, cyclohexyltriisopropylsilyl maleate, bis (triisopropylsilyl) fumarate, methyltriisopropylsilyl fumarate, ethyltriisopropylsilyl fumarate, n-butyltriisopropylsilyl fumarate, Isobutyl triisopropylsilyl fumarate, n-amyl triisopropylsilyl fumarate, isoamyltriisopropylsilyl fumarate, 2-ethylhexyl triisopropylsilyl fumarate, and cyclohexyl triisopropylsilyl fumarate, with triisopropylsilyl (meth) acrylate being particularly preferred. These triisopropylsilyl group-containing monomers may be used alone or in combination of 2 or more.

The silyl ester group-containing resin (B1) is preferably a resin obtained by copolymerizing a monomer (B1) and a monomer (B2) at a mass ratio (B1)/(B2) within a range of 20/80 to 70/30, and more preferably a resin obtained by copolymerizing a monomer (B1) and a monomer (B2) at a mass ratio (B1)/(B2) within a range of 30/70 to 60/40.

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

Examples of the monomer (b2) copolymerizable with the monomer (b1) (or the monomer (b1-1) and/or (b1-2)) include: alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate; alkoxyalkyl (meth) acrylate esters such as 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 2-ethoxyethyl (meth) acrylate; alkylene glycol monomethyl (meth) acrylates such as ethylene glycol monomethyl (meth) acrylate, a (meth) acrylate having an alkoxy group at one molecular end and a polyethylene oxide chain, a (meth) acrylate having a polypropylene oxide chain at one molecular end and an alkoxy group, and propylene glycol monomethyl (meth) acrylate; hydroxyalkyl (meth) acrylates of hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, modified epsilon-caprolactone which is a monoester of (meth) acrylic acid and a 2-membered alcohol having 2 to 8 carbon atoms, allyl alcohol, and (meth) acrylate having a polyethylene oxide chain in which a hydroxyl group is at a molecular terminal; nitrogen-containing monomers such as (meth) acrylonitrile, (meth) acrylamide, N-dimethyl (meth) acrylamide, (meth) acryloylmorpholine, N-isopropyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, N-dimethylaminopropyl (meth) acrylamide, and adducts of glycidyl (meth) acrylate and amines; (meth) acrylates such as benzyl (meth) acrylate and phenyl (meth) acrylate; vinyl chloride; vinylidene chloride; (meth) acrylonitrile; vinyl acetate; butyl vinyl ether; lauryl vinyl ether; n-vinyl pyrrolidone; styrene; vinyl toluene; alpha-methylstyrene, and the like.

As the monomer (b2), for example: vinyl ester compounds such as vinyl propionate and vinyl acetate; carboxyl group-containing monomers such as (meth) acrylic acid, maleic anhydride, fumaric acid, itaconic anhydride, crotonic acid, and β -carboxyethyl (meth) acrylate; epoxy group-containing monomers such as glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3, 4-epoxycyclohexylethyl (meth) acrylate, 3, 4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether; sulfonic acid group-containing monomers such as 2- (meth) acrylamide-2-methylpropanesulfonic acid, allylsulfonic acid, styrenesulfonic acid, sulfoethyl (meth) acrylate, and sodium salts or ammonium salts thereof; a monomer having a phosphate group such as 2- (meth) acryloyloxyethyl acid phosphate; and carbonyl group-containing monomers such as acrolein, diacetone (meth) acrylamide, acetoacetoxyethyl (meth) acrylate, and vinyl alkyl ketones having 4 to 7 carbon atoms (e.g., vinyl methyl ketone, vinyl ethyl ketone, and vinyl butyl ketone).

The above-exemplified monomers (b2) may be used singly or in combination of 2 or more. Among the above-exemplified monomers (b2), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate and the like are particularly preferable.

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

In the present invention, the silyl ester group-containing resin (B1) can be produced by a known polymerization method. The silyl ester group-containing resin (B1) may be any known copolymer such as a random copolymer, a graft copolymer, an inclined structure copolymer, or a block copolymer.

The silyl ester group-containing resin (B1) can be obtained, for example, by copolymerizing the monomer (B1) and the monomer (B2) in the presence of a radical polymerization initiator.

Examples of the radical polymerization initiator used in the copolymerization reaction include: azo compounds such as 2,2 ' -Azobisisobutyronitrile (AIBN), 2 ' -azobis-2-methylbutyronitrile, and dimethyl-2, 2 ' -azobisisobutyrate; diacyl peroxide compounds such as dibenzoyl peroxide, bis (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 peroxyoctanoate; t-amyl peroxide compounds such as t-amyl peroxy-2-ethylhexanoate, t-amyl peroxyacetate, t-amyl peroxyisononanoate, t-amyl peroxybenzoate, t-amyl peroxyacetate, di (t-amyl peroxide), 1-di (t-amyl peroxy) cyclohexane, and the like; t-hexyl peroxide compounds such as t-hexyl peroxy-2-ethylhexanoate, t-hexyl peroxybenzoate, t-hexyl peroxy-isopropyl monocarbonate, t-hexyl peroxy-t-valerate, and t-hexyl peroxyneodecanoate. These polymerization initiators may be used alone or in combination of 2 or more.

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

Further, as a polymerization method for obtaining the silyl ester group-containing resin (B1), for example, there can be mentioned: solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and the like. Among these, the solution polymerization method is particularly preferable in that the silyl ester group-containing resin (B1) can be synthesized easily and accurately.

In the above copolymerization reaction, an organic solvent may be used as necessary. Examples of such organic solvents include: aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate; alcohol solvents such as isopropyl alcohol and butyl alcohol; II

Ether solvents such as alkyl ether, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Among these, aromatic hydrocarbon solvents are preferable, and xylene is particularly preferable.These solvents may be used alone or in combination of 2 or more.

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

[ resin (B2) having a Metal carboxylate Structure ]

The antifouling paint composition of the present invention may contain a resin (B2) having a metal carboxylate structure in addition to the silyl ester group-containing resin (B1) or in place of the silyl ester group-containing resin (B1) (in this specification, the "resin (B2) having a metal carboxylate structure" may be simply referred to as "resin (B2)"). The resin (B2) is not limited to the kind and composition of the resin as long as it has a metal carboxylate structure, and a known resin having a metal carboxylate structure can be used.

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

[ CHEM 8 ]

Examples of the 2-valent metal atom M in the formula (3) include metal atoms such as zinc, copper, magnesium, calcium, iron, and tellurium, and preferably include zinc and copper.

The resin (B2) containing the characteristic group (bb1) having a metal carboxylate structure in which X in the formula (3) is a hydroxyl group can be obtained, for example, by reacting a known resin having a carboxyl group with an oxide or hydroxide of a 2-valent metal in an amount in the range of 0.1 to 1.0 mol relative to 1 mol of the carboxyl group in the resin in the presence of water. The amount of water used in the reaction is preferably in the range of 0.1 to 10.0 mol per 1 mol of the carboxyl group. When the amount of water used is less than 0.1 mol, the structural viscosity may become large, and the treatment of the produced resin (B2) having a metal carboxylate structure may become difficult. On the other hand, when the amount of water used exceeds 10.0 mol, an excessive separation operation of water may be necessary.

Specific examples of the method for producing the resin (B2) containing the characteristic group (bb1) include a method in which a resin having a carboxyl group, water, and a 2-valent metal compound are placed in a reaction vessel and reacted at a temperature of 50 to 150 ℃ for 1 to 20 hours. The reaction can be carried out by adding an appropriate organic solvent to the reaction vessel. Examples of such organic solvents include alcohol-based, ketone-based, ester-based, and ether-based solvents, and these solvents may be used in 1 kind or in combination of 2 or more kinds.

The 2-valent metal compound used for producing the resin (B2) containing the characteristic group (bb1) may be any known compound, and is preferably an oxide, salt or hydroxide of at least 1 metal selected from the group consisting of copper, zinc, calcium, magnesium, iron and tellurium, and more preferably an oxide, salt or hydroxide of zinc or copper, from the viewpoints of cost, toxicity, reactivity and the like.

As the resin having the carboxyl group used for producing the resin (B2) having the characteristic group (bb1), for example, a resin such as a vinyl polymer, polyester, polyurethane, or natural resin can be used, and a vinyl polymer obtained by copolymerizing a carboxyl group-containing unsaturated monomer such as (meth) acrylic acid, maleic acid, fumaric acid, or itaconic acid with another unsaturated monomer such as alkyl (meth) acrylate or styrene can be preferably used in terms of a large degree of freedom in changing the composition.

Examples of the resin (B2) containing the characteristic group (bb2) having a metal carboxylate structure in which X in the above formula (3) is an organic acid residue include a polymer or a copolymer of 2 or more species of unsaturated monomers (bb2m) containing the characteristic group (bb2), a copolymer of 1 or 2 or more species of unsaturated monomers (bb2m) containing the characteristic group (bb2) and 1 or 2 or more species of unsaturated monomers (m1) other than the above unsaturated monomers (bb2m), a resin modified by any method from the above copolymer, and any resin modified by the above copolymer.

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

[ CHEM 9 ]

[ CHEM 10 ]

In the above formula (4) or formula (5), R₁₀、R₁₁And R₁₂Represents a hydrogen atom or a methyl group, A represents an organic acid residue, and M represents a 2-valent metal atom.

Among the unsaturated monomers (bb2m), examples of the method for producing the unsaturated monomer (bb2m-1) represented by the above formula (4) include a method in which a polymerizable unsaturated organic acid such as (meth) acrylic acid, a metal compound such as an oxide, hydroxide or salt of a metal having a valence of 2, and a monobasic organic acid capable of forming an organic acid residue are reacted; a method of reacting a polymerizable unsaturated organic acid with a metal salt of a monobasic organic acid, and the like. These reactions may be carried out in the presence of an organic solvent and/or water, if necessary.

Among the unsaturated monomers (bb2m), examples of the method for producing the unsaturated monomer (bb2m-2) represented by the above formula (5) include a method of reacting a polymerizable unsaturated organic acid such as (meth) acrylic acid with a metal compound such as an oxide, hydroxide or salt of a metal having a valence of 2. The reaction may be carried out in the presence of an organic solvent and/or water, if necessary.

When X in the above formula (3) is an organic acid residue, examples of the organic acid residue include acetic acid, monochloroacetic acid, monofluoroacetic acid, naphthenic acid, propionic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, neodecanoic acid, isostearic acid, palmitic acid, cresol acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, stearic acid, ricinoleic acid, elaidic acid, brassidic acid, erucic acid, α -naphthoic acid, β -naphthoic acid, benzoic acid, 2,4, 5-trichlorophenoxy acetic acid, 2, 4-dichlorophenoxy acetic acid, quinolinecarboxylic acid, nitrobenzoic acid, nitronaphthalene carboxylic acid, occipitalic acid (pulvinic acid), abietic acid, neoabietic acid, dehydroabietic acid, hydrogenated abietic acid, palustric acid, pimaric acid, isopimaric acid, levopimaric acid, dextropimaric acid, sandaracopimaric acid, resinic acid, resin acid, and mixtures thereof, And organic acid residues derived from organic acids such as abietane, pimarane, isopimarane, and compounds having a labdane skeleton. In addition, as the organic acid residue represented by a in the formula (4), organic acid residues derived from the above organic acids can be also exemplified.

Specific examples of the unsaturated monomer (bb2m-1) include: magnesium acetate (meth) acrylate, zinc naphthenate (meth) acrylate, copper acetate (meth) acrylate, copper naphthenate (meth) acrylate, magnesium chloroacetate mono (meth) acrylate, zinc chloroacetate mono (meth) acrylate, copper chloroacetate mono (meth) acrylate, magnesium fluoroacetate mono (meth) acrylate, zinc fluoroacetate mono (meth) acrylate, copper fluoroacetate mono (meth) acrylate, magnesium propionate (meth) acrylate, zinc propionate (meth) acrylate, copper propionate (meth) acrylate, magnesium hexanoate (meth) acrylate, zinc hexanoate (meth) acrylate, copper hexanoate (meth) acrylate, magnesium octanoate (meth) acrylate, zinc octanoate (meth) acrylate, copper octanoate (meth) acrylate, magnesium 2-ethylhexanoate (meth) acrylate, zinc ethylhexanoate (meth) acrylate, copper octanoate (meth) acrylate, magnesium 2-ethylhexanoate (meth) acrylate, zinc 2-ethylhexanoate (, Copper (meth) acrylate 2-ethylhexyl acid, magnesium (meth) acrylate decanoate, zinc (meth) acrylate decanoate, copper (meth) acrylate decanoate, magnesium (meth) acrylate neodecanoate, zinc (meth) acrylate neodecanoate, copper (meth) acrylate neodecanoate, magnesium (meth) acrylate isostearate, zinc (meth) acrylate isostearate, copper (meth) acrylate isostearate, magnesium (meth) acrylate palmitate, zinc (meth) acrylate palmitate, copper (meth) acrylate palmitate, magnesium (meth) acrylate cresolate, zinc (meth) acrylate cresolate, copper (meth) acrylate cresolate, magnesium (meth) acrylate oleate, zinc (meth) acrylate oleate, copper (meth) acrylate oleate, zinc (meth) acrylate stearate, zinc (, Magnesium (meth) acrylate linoleate, (zinc (meth) acrylate linoleate, (copper (meth) acrylate linoleate, (magnesium (meth) acrylate linoleate, (zinc (meth) acrylate linoleate, (copper (meth) acrylate linolenate), (magnesium (meth) acrylate stearynate, (zinc (meth) acrylate stearynate, (copper (meth) acrylate stearynate), (magnesium (meth) acrylate ricinoleate, (zinc (meth) acrylate ricinoleate, (copper (meth) acrylate ricinoleate, (magnesium (meth) acrylate ricinoleate, (zinc (meth) acrylate ricinoleate, (copper (meth) acrylate) ricinoleate, (magnesium (meth) acrylate brassylate, (zinc (meth) acrylate brassylate, (copper (meth) acrylate brassylate, (magnesium (meth) acrylate erucic acid, (zinc (meth) acrylate erucic acid, copper (meth) acrylate, zinc (meth) acrylate ricinoleate, zinc (meth) acrylate, Alpha-magnesium naphthenate, (methyl) acrylic acid alpha-zinc naphthenate, (methyl) acrylic acid alpha-copper naphthenate, (methyl) acrylic acid beta-magnesium naphthenate, (methyl) acrylic acid beta-zinc naphthenate, (methyl) acrylic acid beta-copper naphthenate, (methyl) acrylic acid magnesium benzoate, (methyl) acrylic acid zinc benzoate, (methyl) acrylic acid copper benzoate, (methyl) acrylic acid 2,4, 5-trichlorophenoxy magnesium acetate, (methyl) acrylic acid 2,4, 5-trichlorophenoxy zinc acetate, (methyl) acrylic acid 2,4, 5-trichlorophenoxy copper acetate, (methyl) acrylic acid 2, 4-dichlorophenoxy magnesium acetate, (methyl) acrylic acid 2, 4-dichlorophenoxy zinc acetate, (methyl) acrylic acid 2, 4-dichlorophenoxy copper acetate, copper, Magnesium (meth) acrylate quinolinecarboxylate, zinc (meth) acrylate quinolinecarboxylic acid, copper (meth) acrylate quinolinecarboxylic acid, magnesium (meth) acrylate nitrobenzoate, zinc (meth) acrylate nitrobenzoate, copper (meth) acrylate nitrobenzoate, magnesium (meth) acrylate nitronaphthalene carboxylate, zinc (meth) acrylate nitronaphthalene carboxylate, copper (meth) acrylate nitronaphthalene carboxylate, magnesium (meth) acrylate, zinc (meth) acrylate, copper (meth) acrylate occipitate, and the like. These unsaturated monomers (bb2m-1) can be used by appropriately selecting 1 or 2 or more types as required.

Examples of the unsaturated monomer (bb2m-2) represented by the above formula (5) include: magnesium acrylate ((CH)₂＝CHCOO)₂Mg), magnesium methacrylate ((CH)₂＝C(CH₃)COO)₂Mg), zinc acrylate ((CH)₂＝CHCOO)₂Zn), zinc methacrylate ((CH)₂＝C(CH₃)COO)₂Zn), copper acrylate ((CH)₂＝CHCOO)₂Cu), copper methacrylate ((CH)₂＝C(CH₃)COO)₂Cu), and the like. These unsaturated monomers (b2m-2) may be used by appropriately selecting 1 or 2 or more types as needed, and among these unsaturated monomers, zinc (meth) acrylate is preferably used from the viewpoint of maintaining the antifouling property of the resulting coating film for a long period of time.

The amount of the unsaturated monomer (bb2m-1) used for obtaining the resin (B2) containing the characteristic group (bb2) is preferably in the range of 0.5 to 30.0 mass%, more preferably in the range of 1.0 to 20.0 mass%, based on the mass of the solid content of the resin (B2), from the viewpoint of maintaining the antifouling property of the obtained coating film for a long period of time.

The amount of the unsaturated monomer (bb2m-2) used to obtain the resin (B2) containing the characteristic group (bb2) is preferably in the range of 0.5 to 50.0 mass%, more preferably in the range of 1.0 to 30.0 mass%, based on the mass of the solid content of the resin (B2), from the viewpoint of maintaining the antifouling property of the resulting coating film for a long period of time.

Examples of the resin (B2) containing the characteristic group (B3) having a metal carboxylate structure in which X in the formula (3) is an alcohol residue include: a polymer or a copolymer of 2 or more species of the unsaturated monomer (b3m) having the characteristic group (b3), a copolymer of 1 or 2 or more species of the unsaturated monomer (b3m) having the characteristic group (b3) and 1 or 2 or more species of the unsaturated monomer (m2) other than the unsaturated monomer (b3m), a resin modified by any method from the above copolymer, or any resin modified by the above copolymer.

Examples of the method for producing the unsaturated monomer (b3m) include: a method of reacting a polymerizable unsaturated organic acid such as (meth) acrylic acid, a metal compound such as an oxide, hydroxide or salt of a 2-valent metal, and an alcohol capable of forming an alcohol residue; a method of reacting a polymerizable unsaturated organic acid with a metal alkoxide compound, and the like. These reactions may be carried out in the presence of an organic solvent and/or water, if necessary.

The resin (B2) may be obtained by copolymerizing 1 or 2 or more unsaturated monomers selected from at least 1 unsaturated monomer selected from the group consisting of the unsaturated monomers (bb2m-1), (bb2m-2) and (B3m) and, if necessary, unsaturated monomers (m3) other than these.

The unsaturated monomers (m1), (m2) and (m3) may be the same or different. Examples of the unsaturated monomers (m1), (m2) and (m3) include unsaturated monomers exemplified as the monomer (B2) that can be used for producing the silyl ester group-containing resin (B1).

The copolymerization reaction of the unsaturated monomer (bb2m) and/or (b3m) can be carried out, for example, in the presence of a radical polymerization initiator. As the radical polymerization initiator, the same initiators as those used for the copolymerization reaction of the monomer (B1) and the monomer (B2) in the production of the silyl ester group-containing resin (B1) can be used.

The resin (B2) can be produced, for example, by reacting a known resin having a carboxyl group, a metal compound such as an oxide or hydroxide of a 2-valent metal in an amount of 0.1 to 1.0 mol per 1 mol of the carboxyl group in the resin, and an organic acid, an alcohol compound, water, or the like, as required, at a temperature of 50 to 200 ℃ for 1 to 20 hours. X in the characteristic group having a metal carboxylate structure represented by the formula (3) contained in the resin (B2) produced by the reaction is not particularly limited as long as it is at least 1 group selected from the group consisting of a hydroxyl group, an organic acid residue and an alcohol residue. The reaction may be carried out in the presence of an appropriate organic solvent, and examples of the organic solvent in this case include alcohol-based, ketone-based, ester-based, and ether-based solvents, and these solvents may be used in 1 kind or in combination of 2 or more kinds.

The 2-valent metal compound used for producing the resin (B2) may be a known 2-valent metal compound without particular limitation, and from the viewpoint of cost, toxicity, reactivity, and the like, an oxide, a salt, or a hydroxide of at least 1 metal selected from the group consisting of zinc, copper, magnesium, calcium, iron, and tellurium is preferable, and an oxide, a salt, or a hydroxide of zinc or copper is more preferable.

The resin having a carboxyl group used for producing the resin (B2) may be, for example, a resin such as a vinyl polymer, polyester, polyurethane, or natural resin, and a vinyl polymer obtained by copolymerizing a carboxyl group-containing unsaturated monomer such as (meth) acrylic acid, maleic acid, fumaric acid, or itaconic acid with another unsaturated monomer such as alkyl (meth) acrylate or styrene is preferably used in terms of a large degree of freedom in changing the composition.

The resin (B2) containing the characteristic group (bb2) can be produced by reacting a known resin having a carboxyl group with a 2-valent metal salt of a monovalent organic acid.

In the present invention, X in the characteristic group having a metal carboxylate structure represented by the general formula (3) contained in the resin (B2) having a metal carboxylate structure may be at least 1 group selected from the group consisting of a hydroxyl group, an organic acid residue and an alcohol residue, and the content of a metal atom contained in the metal carboxylate structure is in the range of 0.04 to 3.50 mol/kg, preferably in the range of 0.07 to 3.00 mol/kg, and more preferably in the range of 0.10 to 2.50 mol/kg based on the solid content mass of the resin (B2). When the content of the metal atom is more than 3.50 mol/kg, the retention period of the antifouling property of the obtained coating film may be shortened, and when it is less than 0.04 mol/kg, the antifouling property of the obtained coating film tends to be lowered.

Examples of the production method of the resin (B2) having a metal carboxylate structure other than those described above include a condensation reaction of a metal compound and a compound having 2 or more carboxyl groups in 1 molecule, and an addition polymerization reaction or a condensation reaction using a polyol compound having a metal carboxylate structure.

[ antifouling agent (C) ]

The antifouling paint composition of the present invention contains an antifouling agent (C) in addition to the polyester resin (a), the silyl ester group-containing resin (B1), and/or the resin having a metal carboxylate structure (B2). As the antifouling agent (C), conventionally known antifouling agents can be used, and examples thereof include inorganic compounds, metal-containing organic compounds, metal-free organic compounds, and the like.

Examples of the inorganic compound include: copper compounds such as cuprous oxide, copper powder, copper thiocyanate, copper carbonate, copper chloride, and copper sulfate; zinc compounds such as zinc sulfate and zinc oxide; nickel compounds such as nickel sulfate and copper-nickel alloys.

Examples of the organic compound containing the metal include an organic copper compound, an organic nickel compound, and an organic zinc compound, and maneb, mancozeb, and propineb can be used. Further, examples of the organic copper compound include: copper oxine, copper pyrithione, copper nonylphenolsulfonate, copper bis (ethylenediamine) -bis (dodecylbenzenesulfonate), copper acetate, copper naphthenate, copper bis (pentachlorophenolate), and the like. In addition, examples of the organic nickel-based compound include: nickel acetate, nickel dimethyldithiocarbamate, and the like. Further, examples of the organic zinc-based compound include: zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, zinc pyrithione, zinc ethylenebisdithiocarbamate, and the like.

Examples of the organic compound not containing the metal include: n-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino-1, 3-thiazolidine-2, 4-dione, dithiocyano compound, triazine compound, and the like.

Examples of the N-trihalomethylthiophthalimide include: n-trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide and the like.

Examples of the dithiocarbamic acid include: bis (dimethylthiocarbamoyl) disulfide, ammonium N-methyldithiocarbamate, ammonium ethylenebis (dithiocarbamate), metiram and the like.

Examples of the N-arylmaleimide include: n- (2,4, 6-trichlorophenyl) maleimide, N-4-tolylmaleimide, N-3-chlorophenylmaleimide, N- (4-N-butylphenyl) maleimide, N- (anilinophenyl) maleimide, N- (2, 3-xylyl) maleimide, 2, 3-dichloro-N- (2 ', 6' -diethylphenyl) maleimide, 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, 3- (4-methylbenzylideneamino) -1, 3-thiazolidine-2, 4-dione, 3- (2-hydroxybenzylideneamino) -1, 3-thiazolidine-2, 4-dione, 3- (4-dimethylaminobenzylidene amino) -1, 3-thiazoline-2, 4-dione, 3- (2, 4-dichlorobenzylideneamino) -1, 3-thiazolidine-2, 4-dione, and the like.

Examples of the dithiocyano compound include: dithiocyanomethane, dithiocyanoethane, 2, 5-dithiocyanothiophene, and the like.

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

Examples of the organic compound not containing the metal include, in addition to the above-mentioned organic compounds exemplified above: 2,4,5, 6-tetrachloroisophthalonitrile, N-dimethyldichlorophenylurea, 4, 5-dichloro-2-N-octyl-3- (2H) isothiazolinone, N-dimethyl-N' -phenyl- (N-fluorodichloromethylthio) sulfamide, tetramethylthiuram disulfide, 3-iodo-2-propynylbutylcarbamate, 2- (methoxycarbonylamino) benzimidazole, 2,3,5, 6-tetrachloro-4- (methylsulfonyl) pyridine, diiodomethyl-p-tolylsulfone, bisdimethyldithiocarbamoylzinc ethylene bisdithiocarbamoylhexanoate, phenyl (bispyridine) bismuth dichloride, 2- (4-thiazolyl) benzimidazole, triphenylboropyridine-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 alone or in combination of 2 or more of the above-exemplified compounds. Among the above-exemplified compounds, cuprous oxide is preferably used, and cuprous oxide and copper pyrithione are particularly preferably used in combination, from the viewpoint of exhibiting stable antifouling performance.

[ antifouling paint composition and coated article having coating film thereof ]

The antifouling paint composition comprises a polyester resin (A), a silyl ester group-containing resin (B1) and/or a resin (B2) having a metal carboxylate structure, and an antifouling agent (C), and is characterized in that the polyester resin (A) has a structural unit represented by the formula (1) in the resin skeleton, and the total mass ratio of the polyester resin (A), the silyl ester group-containing resin (B1), and the resin (B2) having a metal carboxylate structure is in the range of 3/97 to 80/20.

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

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

In the antifouling paint composition of the present invention, 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), the silyl ester group-containing resin (B1), and the resin having a metal carboxylate structure (B2). 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 over a long period of time, and when the content of the antifouling agent (C) is more than 500% by mass, the properties of the obtained coating film may be deteriorated, and defects such as peeling and swelling may occur.

In the antifouling paint composition of the present invention, in addition to the polyester resin (a), the silyl ester group-containing resin (B1) and/or the resin having a metal carboxylate structure (B2), and the antifouling agent (C), there may be blended, as required: additives such as pigments, dyes, dehydrating agents, plasticizers, thixotropic agents (anti-sagging agents), antifoaming agents, antioxidants, and the like; a resin other than the polyester resin (a), the silyl ester group-containing resin (B1), and the resin having a metal carboxylate structure (B2); an organic acid; solvents and the like are used for various components of general coating compositions. These components may be used alone or in combination of 2 or more.

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

The content of the pigment in the antifouling paint composition of the present invention is preferably in the range of 0.05 to 1000 mass%, more preferably in the range of 1 to 500 mass%, based on the total mass of the polyester resin (a), the silyl ester group-containing resin (B1), and the resin having a metal carboxylate structure (B2).

The dehydrating agent is a component contributing to the improvement of the storage stability of the antifouling paint composition. Examples of such a dehydrating agent include inorganic materials such as anhydrous gypsum, hemihydrate gypsum (calcined gypsum), synthetic zeolite adsorbents (for example, "Molecular sieve" (trade name)), orthoesters (for example, methyl orthoformate, methyl orthoacetate, orthoborate, etc.), silicates, isocyanates, and the like. Among these, anhydrous gypsum and hemihydrate gypsum (plaster of Paris) are preferred as the inorganic dehydrating agents. These dehydrating agents may be used alone in 1 kind, or 2 or more kinds may be used in combination. The content of the dehydrating agent in the antifouling paint composition may be appropriately adjusted, but is preferably in the range of 0 to 100% by mass, more preferably in the range of 0.5 to 25% by mass, based on the total mass of the polyester resin (a), the silyl ester group-containing resin (B1), and the resin having a metal carboxylate structure (B2).

The plasticizer is a component contributing to improvement in crack resistance, water resistance, and the like of the obtained antifouling coating film. Examples of such plasticizers include: tricresyl phosphate, dioctyl phthalate, chlorinated paraffins, mobile paraffins, n-paraffins, chlorinated paraffins, polybutenes, terpene phenols, tricresyl phosphate (TCP), polyvinyl ethyl ether, and the like. These plasticizers may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When a plasticizer is added to the antifouling paint composition of the present invention, the content of the plasticizer in the antifouling paint composition is preferably in the range of 0.5 to 10% by mass, more preferably in the range of 1 to 5% by mass, based on the total mass of the polyester resin (a), the silyl ester group-containing resin (B1), and the resin having a metal carboxylate structure (B2).

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

Examples of the thixotropic agent include: organic waxes (for example, polyethylene wax, oxidized polyethylene wax, polyamide wax, amide wax, hydrogenated castor oil wax, etc.), organoclay compounds (for example, amine salts of Al, Ca, Zn, stearate salts, lecithin salts, alkyl sulfonate salts, etc.), bentonite, synthetic fine powder silica, and the like. These thixotropic agents may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When a thixotropic agent is added to the antifouling paint composition of the present invention, the content of the thixotropic agent in the antifouling paint composition may be appropriately adjusted, and is, for example, in the range of 0.25 to 50% by mass based on the total mass of the polyester resin (a), the silyl ester group-containing resin (B1), and the resin having a metal carboxylate structure (B2).

The antifouling paint composition of the present invention may contain 1 or 2 or more kinds of other resins as necessary, in addition to the polyester resin (a), the silyl ester group-containing resin (B1), and the resin having a metal carboxylate structure (B2). Examples of such resins include acrylic resins, acrylic silicone resins, epoxy resins, fluorine resins, polybutene resins, silicone rubbers, polyurethane resins, polyamide resins, vinyl chloride copolymer resins, chlorinated rubbers, chlorinated olefin resins, styrene-butadiene copolymer resins, ketone resins, ethylene-vinyl acetate copolymer resins, chlorinated vinyl resins, alkyd resins, coumarone resins, terpene phenol resins, and petroleum resins, which are widely used as matrix resins for antifouling paints.

The antifouling paint composition of the present invention may contain a known rosin compound. Examples of such rosin-based compounds include: rosin, rosin derivatives, rosin metal salts, and the like. Further, examples of the rosin include: tall rosin, rubber rosin, wood rosin, and the like. Examples of the rosin derivative include hydrogenated rosin, maleated rosin obtained by reacting rosin with maleic anhydride, formylated rosin, and polymerized rosin. Further, examples of the rosin metal salt include: zinc rosinate, calcium rosinate, copper rosinate, magnesium rosinate, and the reaction product of metal compound and rosin. These rosin-based compounds may be used alone or in combination of 2 or more.

When a rosin-based compound is added to the antifouling paint composition of the present invention, the content of the rosin-based compound in the antifouling paint composition is not particularly limited, and is, for example, preferably 50% by mass or less, more preferably 30% by mass or less, based on the total mass of the polyester resin (a), the silyl ester group-containing resin (B1), and the resin having a metal carboxylate structure (B2).

The antifouling paint composition of the present invention may contain an organic solvent usually used as a solvent for an antifouling paint, such as an aliphatic solvent, an aromatic solvent (e.g., xylene, toluene, etc.), a ketone solvent (e.g., methyl isobutyl ketone, cyclohexanone, etc.), an ester solvent, an ether solvent (e.g., propylene glycol monomethyl ether acetate, etc.), an alcohol solvent (e.g., isopropyl alcohol, etc.), and the like. The amount of the organic solvent may be appropriately adjusted, and for example, may be in the range of 20 to 90 mass% of the total solid content of the antifouling paint composition, or may be added depending on the workability at the time of coating.

The antifouling paint composition of the present invention can be produced by the same method as that for a known antifouling paint composition. For example, the polyester resin (a), the silyl ester group-containing resin (B1), and/or the resin having a metal carboxylate structure (B2), the antifouling agent (C), and the organic solvent or the additive, if necessary, may be added to a stirring tank at once or in sequence, and then stirred and mixed.

The coated article of the present invention is an article having a coating film of the antifouling paint composition of the present invention. The coated article can be obtained by a method including a step of applying or impregnating the antifouling paint composition to the surface of a substrate 1 to a plurality of times, and a step of drying the applied or impregnated antifouling paint composition.

Examples of the substrate include substrates that come into contact with seawater or fresh water (e.g., constantly or intermittently), specifically, underwater structures; a marine planking or bottom; a water conduit or cooling pipe for a power generation plant; fishing nets, fishing gears for cultivation or setting, or suspended matters used in these; fishing net accessories such as ropes and the like. The film thickness of the coating film obtained from the antifouling paint composition of the present invention can be suitably adjusted in consideration of the consumption rate (dissolution rate) of the coating film, and for example, the film thickness (μm) per 1 coating can be about 30 to 250 μm/time, preferably about 75 to 150 μm/time, and can be about 60 to 500 μm by further coating 2 or more times as necessary.

In order to obtain the coated article, the antifouling paint composition of the present invention may be applied to the surface of the substrate by a method such as brush coating, spray coating, roll coating, or dipping, on the surface coated with the primer, the anticorrosive paint, and if necessary, the binder paint. The antifouling paint composition of the present invention can be repeatedly applied to the surface of a conventional antifouling coating film. The coating film may be dried at room temperature or, if necessary, may be dried by heating at a temperature of about 100 ℃.

[ examples ] A method for producing a compound

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the examples. In the following examples, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

Production of polyester resin (A)

Production example 1 production of polyester resin (A1)

415.3 parts of PA, 235.7 parts of NPG, 237.9 parts of DEG, and 161.6 parts of lactide as lactic acid were charged into a 2L reactor equipped with a thermometer, a stirrer, and a rectifying column, and the temperature of the contents of the reactor was raised to 160 ℃. Then, the temperature of the contents of the reaction apparatus was raised from 160 ℃ to 230 ℃ over 3 hours, the temperature of the contents was maintained at 230 ℃ for 2 hours, and then the distillation column was changed to a water separator, about 50.0 parts of xylene was charged into the reaction apparatus, and polycondensation was carried out while removing the water of condensation by azeotroping water with xylene. After confirming that the acid value of the polyester resin produced was 3.0mgKOH/g or less, heating was stopped and cooling was started, and xylene was added to dilute the mixture, thereby obtaining a polyester resin (A1) solution having a solid content of 70%. The acid value of the resin was measured by titration of 1/10 equivalents of an alcohol solution of potassium hydroxide using a mixed solution of toluene and isopropyl alcohol (mass ratio 1/1) as a solvent dissolution measurement sample.

The relationship between the compounds corresponding to the abbreviations of the polyester raw materials in the present specification is shown below.

PA; phthalic anhydride, iPA; isophthalic acid, AD; adipic acid, HHPA; hexahydrophthalic anhydride, EG; ethylene glycol, PG; propylene glycol, NPG; neopentyl glycol, 1, 6-HD; 1, 6-hexanediol, BEPG; 2-butyl-2-ethyl-1, 3-propanediol, CHDM; 1, 4-cyclohexanedimethanol, DEG; diethylene glycol, TEG; triethylene glycol, Tetra EG; tetraethylene glycol, DPG; dipropylene glycol, TMP; trimethylolpropane, G; glycerol, PE; pentaerythritol, LA; lactide of lactic acid, GL; glycolide

Production examples 2 to 8 and 13 to 17 production of polyester resins (A2) to (A8) and (A13) to (A17)

Resin solutions of the respective polyester resins (a2) to (A8) and (a13) to (a17) having a solid content of 70% were obtained in the same manner as in production example 1, except that the acid component and the alcohol component in production example 1 were blended as shown in table 1-1.

Production example 9 production of polyester resin (A9)

340.9 parts of iPA, 215.6 parts of NPG, 217.7 parts of DEG, and 147.8 parts of lactide as lactic acid were charged into a 2L reactor equipped with a thermometer, a stirrer, and a rectifying column, and the temperature of the contents of the reactor was raised to 160 ℃. Subsequently, the temperature of the contents of the reaction apparatus was raised from 160 ℃ to 230 ℃ over 3 hours, the temperature of the contents was maintained at 230 ℃ for 2 hours, and then the distillation column was changed to a water separator, and about 45 parts of xylene was charged into the reaction apparatus, and polycondensation was carried out while removing the water of condensation by azeotroping water with xylene. After confirming that the acid value of the resulting polyester resin was 3.0mgKOH/g or less, the temperature of the contents was cooled to 160 ℃. Further 152.0 parts of PA was added, and after the addition reaction (half-esterification) was carried out by keeping at 160 ℃ for 1 hour, cooling was started. After cooling to 130 ℃, xylene was added to dilute the mixture, thereby obtaining a resin solution of a polyester resin (a9) having a solid content of 70%.

Production example 10 production of polyester resin (A10)

292.8 parts of iPA, 185.2 parts of NPG, 186.9 parts of DEG, and 127.0 parts of lactide as lactic acid were charged into a 2L reactor equipped with a thermometer, a stirrer, and a rectifying column, and the temperature of the contents of the reactor was raised to 160 ℃. Subsequently, the temperature of the contents of the reaction apparatus was raised from 160 ℃ to 230 ℃ over 3 hours, the temperature of the contents was maintained at 230 ℃ for 2 hours, and then the distillation column was changed to a water separator, and about 45 parts of xylene was charged into the reaction apparatus, and polycondensation was carried out while removing the water of condensation by azeotroping water with xylene. After confirming that the acid value of the resulting polyester resin was 3.0mgKOH/g or less, the temperature of the contents was cooled to 160 ℃. 276.1 parts of HHPA were further added, and after the addition reaction (half-esterification) was carried out by keeping at 160 ℃ for 1 hour, cooling was started. After cooling to 130 ℃, xylene was added to dilute the mixture, thereby obtaining a resin solution of a polyester resin (a10) having a solid content of 70%.

Production example 11 production of polyester resin (A11)

415.3 parts of PA, 235.7 parts of NPG, 237.9 parts of DEG, and 229.5 parts of an 88 mass% aqueous lactic acid solution were charged into a 2L reactor equipped with a thermometer, a stirrer, and a rectifying column, and the temperature of the contents of the reactor was raised to 130 ℃. Subsequently, the temperature of the contents of the reaction apparatus was raised from 130 ℃ to 160 ℃ over 3 hours, the temperature of the contents was maintained at 230 ℃ for 2 hours, and then the distillation column was changed to a water separator, about 50.0 parts of xylene was charged into the reaction apparatus, and polycondensation was carried out while removing the water of condensation by azeotroping water with xylene. After confirming that the acid value of the polyester resin produced was 3.0mgKOH/g or less, heating was stopped and cooling was started, and xylene was added to dilute the mixture, thereby obtaining a resin solution of a polyester resin (A11) having a solid content of 70%.

Production example 12 production of polyester resin (A12)

217.4 parts of PA, 18.2 parts of EG, 205.7 parts of PE, 625.3 parts of soybean oil fatty acid, 28.2 parts of lactide as lactic acid, and 50.0 parts of xylene were charged into a 2L reactor equipped with a thermometer, a stirrer, and a water separator, and the temperature of the contents of the reactor was raised to 160 ℃ and held for 1 hour. Subsequently, the temperature of the contents of the reaction apparatus was raised from 160 ℃ to 240 ℃ over 4 hours, and polycondensation was carried out while removing the generated condensation water at 240 ℃. After confirming that the acid value of the resin was about 3.0mgKOH/g or less, heating was stopped and cooling was started, and xylene was added to dilute the resin, thereby obtaining a resin solution of a polyester resin (A12) having a solid content of 70%.

The resin acid values and the weight average molecular weights of the polyester resins (a1) to (a17) obtained in the above production examples are shown in table 1-1 together with the amounts blended in the production examples.

[ TABLE1 ]

Production example 1') production of polyester resin (A1

428.7 parts of PA, 243.3 parts of NPG, 245.7 parts of DEG and 134.4 parts of Glycolide (GL) were charged into a 2L reactor equipped with a thermometer, a stirrer and a rectifying column, and the temperature of the contents of the reactor was raised to 160 ℃. Then, the temperature of the contents of the reaction apparatus was raised from 160 ℃ to 230 ℃ over 3 hours, the temperature of the contents was maintained at 230 ℃ for 2 hours, and then the distillation column was changed to a water separator, about 50.0 parts of xylene was charged into the reaction apparatus, and polycondensation was carried out while removing the water of condensation by azeotroping water with xylene. After confirming that the acid value of the resulting polyester resin was 3.0mgKOH/g or less, heating was stopped and cooling was started, and xylene was added to dilute the mixture, thereby obtaining a polyester resin (A1') solution having a solid content of 70%.

Production of polyester resins (A2 ') - (A8 ') - (A13 ') to (A18') production examples 2 ' to 8', 13 ' to 18

Resin solutions of the respective polyester resins (A2 ') (A8'), (A13 ') (A18') having a solid content of 70% were obtained in the same manner as in production example 1 'except that the acid component and the alcohol component in production example 1' were blended as shown in Table 1-2.

Production example 9') production of polyester resin (A9

To a 2L reactor equipped with a thermometer, a stirrer, and a rectifying column, 351.0 parts of iPA, 222.0 parts of NPG, 224.1 parts of DEG, and 122.6 parts of glycolide were charged, and the temperature of the contents of the reactor was raised to 160 ℃. Subsequently, the temperature of the contents of the reaction apparatus was raised from 160 ℃ to 230 ℃ over 3 hours, the temperature of the contents was maintained at 230 ℃ for 2 hours, and then the distillation column was changed to a water separator, and about 45 parts of xylene was charged into the reaction apparatus, and polycondensation was carried out while removing the water of condensation by azeotroping water with xylene. After confirming that the acid value of the resulting polyester resin was 3.0mgKOH/g or less, the temperature of the contents was cooled to 160 ℃. Further 156.4 parts of PA was added, and after the addition reaction (half-esterification) was carried out by keeping at 160 ℃ for 1 hour, cooling was started. After cooling to 130 ℃, xylene was added to dilute the mixture, thereby obtaining a resin solution of the polyester resin (a 9') having a solid content of 70%.

Production example 10') production of polyester resin (A10

300.2 parts of iPA, 189.9 parts of NPG, 191.7 parts of DEG and 104.9 parts of glycolide were charged into a 2L reactor equipped with a thermometer, a stirrer and a rectifying column, and the temperature of the contents of the reactor was raised to 160 ℃. Subsequently, the temperature of the contents of the reaction apparatus was raised from 160 ℃ to 230 ℃ over 3 hours, the temperature of the contents was maintained at 230 ℃ for 2 hours, and then the distillation column was changed to a water separator, and about 45 parts of xylene was charged into the reaction apparatus, and polycondensation was carried out while removing the water of condensation by azeotroping water with xylene. After confirming that the acid value of the resulting polyester resin was 3.0mgKOH/g or less, the temperature of the contents was cooled to 160 ℃. 278.5 parts of HHPA was further added, and after the addition reaction (half-esterification) was carried out by keeping at 160 ℃ for 1 hour, cooling was started. After cooling to 130 ℃, xylene was added to dilute the mixture, thereby obtaining a resin solution of the polyester resin (a 10') having a solid content of 70%.

Production example 11') production of polyester resin (A11

428.7 parts of PA, 243.3 parts of NPG, 245.7 parts of DEG and 176.1 parts of glycolic acid were charged into a 2L reactor equipped with a thermometer, a stirrer and a rectifying column, and the temperature of the contents of the reactor was raised to 130 ℃. Subsequently, the temperature of the contents of the reaction apparatus was raised from 130 ℃ to 160 ℃ over 3 hours, the temperature of the contents was maintained at 230 ℃ for 2 hours, and then the distillation column was changed to a water separator, about 50.0 parts of xylene was charged into the reaction apparatus, and polycondensation was carried out while removing the water of condensation by azeotroping water with xylene. After confirming that the acid value of the polyester resin produced was 3.0mgKOH/g or less, heating was stopped and cooling was started, and xylene was added to dilute the mixture, thereby obtaining a resin solution of a polyester resin (A11') having a solid content of 70%.

Production example 12') production of polyester resin (A12

217.4 parts of PA, 18.2 parts of EG, 205.7 parts of PE, 625.3 parts of soybean oil fatty acid, 22.7 parts of glycolide, and 50.0 parts of xylene were charged into a 2L reactor equipped with a thermometer, a stirrer, and a water separator, and the temperature of the contents of the reactor was raised to 160 ℃ and held for 1 hour. Subsequently, the temperature of the contents of the reaction apparatus was raised from 160 ℃ to 240 ℃ over 4 hours, and polycondensation was carried out while removing the generated condensation water at 240 ℃. After confirming that the acid value of the resin was not more than about 3.0mgKOH/g, the heating was stopped and the cooling was started, and xylene was added to dilute the resin, thereby obtaining a resin solution of the polyester resin (A12') having a solid content of 70%.

The resin acid values and the weight average molecular weights of the polyester resins (A1') to (A18') obtained in the above-mentioned production examples are shown in Table 1-2 together with the amounts blended in the production examples.

[ TABLE 2 ]

Production of silyl ester group-containing resin (B1)

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

40 parts of xylene was charged into a beaker with a stirrer, the liquid phase temperature was maintained at 140 ℃, and a mixture of each unsaturated monomer shown in Table 2 and 1 part of a peroxide-based polymerization initiator "Perbutyl I" (trade name) manufactured by Nichisu oil Co., Ltd was added dropwise to the beaker over 3 hours, and after completion of the dropwise addition, the temperature was maintained for 30 minutes. Subsequently, a mixture of 10 parts of xylene and 1 part of "perbutylI" (trade name) was added dropwise over 20 minutes, and after stirring was continued at that temperature for 2 hours, cooling of the liquid phase was started. Further, xylene was added to the beaker to prepare a solution of the resulting resin so that the solid content concentration became 50 mass%, thereby obtaining a resin solution containing the silyl ester-based resin (B1-1).

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

A resin solution (solid content concentration 50 mass%) of the silyl ester group-containing resins (B1-2) and (B1-3) was obtained in the same manner as in production example 18, except that the unsaturated monomers shown in Table 2 were used in combination.

[ TABLE 3 ]

TABLE 2

The numerical values of the monomers in the respective production examples are parts by mass.

Production of resin (B2) having Metal carboxylate Structure

Production example 21 production of resin (B2-1) having Metal carboxylate Structure

A reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, and a dropping pump was charged with 241.7 parts of xylene, 197.5 parts of butyl acetate, and 241.7 parts of n-butanol, and the temperature of the contents in the reaction vessel was raised to 105 ℃ while stirring the contents. Then, a mixed solution containing 104.2 parts of methacrylic acid, 304.4 parts of ethyl acrylate, 272.4 parts of methoxyethyl acrylate, and 54.5 parts of 2, 2-azobis (2-methylbutyronitrile) was added dropwise at a constant rate for 4 hours by means of a dropping pump into a reaction vessel kept at 105 ℃ and uniformly stirred. After the completion of the dropwise addition of the mixed solution, the temperature of the contents in the reaction vessel was kept at 105 ℃ for 1 hour, thereby obtaining an acrylic resin solution.

Further, 49.7 parts of zinc oxide and 34.0 parts of deionized water were added to the obtained resin solution, and the mixture was continuously stirred at 100 ℃ for 20 hours, whereby a resin solution of a resin having a metal carboxylate structure (B2-1) which was not volatilized or at about 50% was obtained. The content of the metal atom contained in the resin (B2-1) (hereinafter, simply referred to as "metal content") was 0.79 mol/kg.

Production example 22 production of resin (B2-2) having Metal carboxylate Structure

563.0 parts of xylene and 140.7 parts of n-butanol were added to a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser and a dropping pump, and the temperature of the mixed solution in the reaction vessel was maintained at 110 ℃ to 120 ℃. To this solution was added dropwise a mixed solution containing 281.5 parts of ethyl acrylate, 117.3 parts of 2-ethylhexyl acrylate, 70.4 parts of acrylic acid, and 37.5 parts of 2, 2-azobis (2-methylbutyronitrile) at a constant rate over 3 hours. After the completion of the dropwise addition of the mixed solution, the temperature of the mixed solution was continuously maintained at from 110 ℃ to 120 ℃ for 2 hours, thereby obtaining an acrylic resin solution.

Then, 236.4 parts of naphthenic acid and 82.8 parts of copper hydroxide were added to the obtained resin solution, and the temperature was raised to 120 ℃ and held for 2 hours. During this time, the water produced was removed (dehydration amount: about 30 parts), and a resin solution of a resin having a metal carboxylate structure (B2-2) having a nonvolatile content of about 50% was obtained. The metal content in the resin (B2-2) was 1.08 mol/kg.

The content of metals such as zinc and copper in the resin was determined by the fluorescent X-ray method.

[ TABLE 4 ]

TABLE 3

(Note 1) (CH)₂＝CHCOO)₂Zn

(Note 2)2, 2-azobis (2-methylbutyronitrile)

Preparation and various tests of antifouling coating composition

Examples 1 to 28 and comparative examples 1 to 8, and examples 29 to 57 and comparative examples 9 to 16

Evaluation of

The resin solutions of the polyester resins (A1) to (A17) and (A1') to (A18'), the resin solutions of the silyl ester group-containing resins (B1-1) to (B1-3), the resins (B2-1) and (B2-2) having metal carboxylate structures, the antifouling agents, the pigments and the like were blended in the blending compositions shown in tables 4-1 to 4-4, and mixed and dispersed at a stirring speed of about 2000rpm by using a homogenizer. After dispersion, DISPARLON a630 to 20XN (anti-sagging agent, manufactured by nakeda chemical corporation) and a solvent were added thereto, followed by dispersion and stirring to prepare coating compositions (E1) to (E73). The prepared coating compositions were subjected to the following antifouling performance tests (test results shown in tables 5-1 to 5-4), adhesion tests (test results shown in tables 6-1 to 6-4), and cracking resistance tests (test results shown in tables 7-1 to 7-4).

< antifouling Property test >

An epoxy rust preventive paint was spray-coated on both surfaces of a sand-blast-treated steel sheet (100 mm. times.300 mm. times.2 mm) so as to have a dry film thickness of 200 μm, and an epoxy adhesive coating was further coated so as to have a dry film thickness of 100 μm. Each coating composition was applied to both surfaces of the coated plate by spray coating 4 times so that the dry film thickness became 480 μm on one surface, and the coated plate was dried in a constant temperature and humidity chamber at a temperature of 20 ℃ and a humidity of 75% for 1 week to prepare test pieces. Using this test piece, the test film was immersed in seawater for 60 months at the level of trefoil county, south yokovich, and the proportion of the area occupied by fouling organisms (area of fouling) on the test film was measured over time.

Very good: (acceptable) No attached organisms were observed

O: (qualified) the occupied area of attached organisms is less than 5 percent

And (delta): the occupied area of (unqualified) attached organisms is more than 5% and less than 30%

X: the occupied area of (unqualified) attached organisms is more than 30%

< adhesion test >

An epoxy anticorrosive paint was spray-coated on a sand-blast-treated steel sheet (120mm × 120mm × 1mm) having flexibility so as to be attachable to a cylindrical drum (diameter 500mm × height 240mm) to have a dry film thickness of 200 μm, and an epoxy adhesive coating was further coated to have a dry film thickness of 100 μm. Each coating composition was applied to one surface of the coated steel sheet by spray coating 4 times so that the dry film thickness became 480 μm, and the steel sheet was dried in a constant temperature and humidity room at a temperature of 20 ℃ and a humidity of 75% for 1 week to prepare a test piece. The test piece was mounted on the cylindrical drum described above, and the cylindrical drum was rotated for 24 months in 16 seas at 500mm under the sea surface of good gulf in Bingkui county. The test piece was collected from the sea over time, and a 5mm × 5mm checkerboard was formed, and the adhesiveness by tape peeling was evaluated. The evaluation was set to ISO 2409: 1992 as a benchmark.

Very good: (acceptable) Table1Classification 0.1

O: (Accept) Table1Classification 2

And (delta): (unqualified) Table1Classification 3

X: (unqualified) Table1Classification 4 & 5

< crack resistance test >

The test piece used in the adhesion test was visually observed for the coating film, and the presence or absence of cracking was examined.

Very good: (acceptable) No cracking was observed

O: (acceptable) slight fine cracking was observed on the surface of the coating film

And (delta): (failure) although the film did not reach the substrate, many fine and clear cracks were observed on the surface of the coating film

X: (failure) cracking of the substrate was observed

[ TABLE 5]

[ TABLE 6 ]

[ TABLE 7 ]

[ TABLE 8 ]

[ TABLE 9 ]

TABLE 5-1 antifouling Property test

[ TABLE 10 ]

TABLE 5-2 antifouling Property test

[ TABLE 11 ]

TABLE 5-3 antifouling Property test

[ TABLE 12 ]

TABLE 5-4 antifouling Property test

[ TABLE 13 ]

TABLE 6-1 adhesion test

[ TABLE 14 ]

TABLE 6-2 adhesion test

[ TABLE 15 ]

TABLE 6-3 adhesion test

[ TABLE 16 ]

TABLE 6-4 adhesion test

[ TABLE 17 ]

TABLE 7-1 crack resistance test

[ TABLE 18 ]

TABLE 7-2 crack resistance test

[ TABLE 19 ]

TABLE 7-3 crack resistance test

[ TABLE 20 ]

TABLE 7-4 crack resistance test

Claims

1. An antifouling coating composition comprising a polyester resin (A), a silyl ester group-containing resin (B1) and/or a resin having a metal carboxylate structure (B2), and an antifouling agent (C),

the polyester resin (A) has a structural unit represented by the following formula (1) in the resin skeleton, the total mass of the structural units represented by the following formula (1) is within the range of 2-47.7 mass% based on the mass of the polyester resin (A), and the weight average molecular weight is within the range of 600-8000,

the mass ratio of the polyester resin (A) to the total of the silyl ester group-containing resin (B1) and the resin having a metal carboxylate structure (B2) is in the range of 3/97 to 80/20,

[ CHEM 1 ]

In the formula, R₀Represents a hydrogen atom or a methyl group, m represents an integer of 1 to 100,

the silyl ester group-containing resin (B1) is a copolymer of 1 or 2 or more monomers (B1) represented by the following formula (2) and 1 or 2 or more monomers (B2) other than the monomer (B1),

[ CHEM 2 ]

In the formula, R₄Represents a hydrogen atom or a methyl group, R₁、R₂And R₃Each independently represents a hydrocarbon group, R₅Represents a hydrogen atom or R₆-O-CO-, wherein R₆Represents an organic group or-SiR₇R₈R₉Silyl radical of formula R₇、R₈And R₉Each independently represents a hydrocarbon group,

the resin (B2) having a metal carboxylate structure has a characteristic group having a metal carboxylate structure represented by the following formula (3), wherein the content of a metal atom contained in the resin (B2) having a metal carboxylate structure is in the range of 0.04 to 3.50 mol/kg based on the solid content mass of the resin (B2),

[ CHEM 3 ]

Wherein M represents a 2-valent metal atom, X represents at least 1 group selected from the group consisting of a hydroxyl group, an organic acid residue and an alcohol residue,

the resin having a carboxyl group used for the production of the resin (B2) uses vinyl polymer, polyester, polyurethane.

2. The antifouling paint composition according to claim 1, wherein the polyester resin (A) is produced using at least one raw material mixture comprising at least 1 component selected from the group consisting of lactic acid, lactide of lactic acid, and polylactic acid, and at least one raw material mixture comprising at least 1 component selected from the group consisting of glycolic acid, glycolide, and polyglycolic acid, and has an acid value in the range of 0.1 to 120 KOHmg/g.

3. The antifouling paint composition according to claim 1, wherein the polyester resin (A) is a polyester resin having no metal carboxylate structure.

4. A coated article having a coating film of the antifouling paint composition according to any one of claims 1 to 3.