JP2018009136A - Antifouling coating composition, and coated article having film thereof - Google Patents

Abstract

An object of the present invention is to provide an antifouling film capable of maintaining an excellent antifouling property for a long period of time and capable of forming an antifouling coating film which is less prone to coating film defects such as coating film peeling, blistering and cracking. An object of the present invention is to provide a coated article such as a fishing net, a ship, a marine or a gulf structure having a soiling paint composition and a coating film of the antifouling paint composition.
The present invention provides an antifouling paint composition comprising a polyester resin having a specific structural unit in a 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.
[Selection figure] None

Description

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

In recent years, various types of resins having hydrolyzability in seawater have been studied as antifouling coating resins replacing organic tin-containing copolymers that are feared for marine pollution. A coating film formed on the surface of a structure that comes into contact with seawater such as a ship using an antifouling paint composition containing a resin having hydrolyzability (that is, a hydrolyzable antifouling paint composition) When it comes into contact with seawater, the hydrolyzable resin gradually hydrolyzes and the coating film dissolves in the seawater, and the coating surface continues to be renewed. It becomes. As a resin having hydrolyzability in seawater, many hydrolyzable antifouling paint compositions containing a trialkylsilyl ester group-containing resin or a resin having a metal carboxylate structure have been proposed so far. However, the trialkylsilyl ester group-containing resin has different hydrolysis rates depending on the type of alkyl group of the trialkylsilyl ester group and the structure of the resin, and the resin having a metal carboxylate structure is different from the type of metal and the resin. Since the hydrolysis rate varies depending on the resin structure, the antifouling coating composition using these hydrolyzable resins often has difficulty in controlling the dissolution rate of the resulting coating film in seawater.
Then, the method of controlling the dissolution rate of a coating film with the hydrolyzable antifouling paint composition which used such a hydrolyzable resin in combination with rosin or a rosin derivative has been studied (Patent Documents 1 to 6). reference). By using a hydrolyzable resin in combination with rosin or a rosin derivative, the dissolution rate of the coating film can be controlled to some extent, but when the amount of rosin or rosin derivative used is small, There was a problem that the solubility of the coating film was not sufficiently obtained, and the antifouling performance of the coating film was difficult to be sustained. On the other hand, when the amount of rosin or rosin derivative used is large, the antifouling performance is improved by increasing the dissolution rate of the coating film in seawater, but the physical properties and adhesion of the coating film are reduced. There is a risk that coating film defects such as coating film peeling, blistering, and cracks are likely to occur, and it is difficult to maintain antifouling performance for a long period of time.

  And in order to solve these problems, the antifouling coating composition which contains a polyester resin and a trialkylsilyl ester group containing resin by the mass ratio in a specific range is proposed (refer patent document 7). . According to such an antifouling coating composition, while having an excellent antifouling property, it is possible to form an antifouling coating that hardly causes coating film defects such as blisters and cracks, but the antifouling coating is exposed. Depending on the sea area and paint composition used, the coating film performance may be slightly insufficient in terms of maintaining antifouling performance for a long period of time, and further improvements are required.

Japanese Patent Laid-Open No. 10-30071 JP 2002-53797 A JP 2011-26357 A JP 2011-32489 A International Publication No. 2011/046087 JP-A-9-286933 International Publication No. 2015/156073

  An object of the present invention is to provide an antifouling paint composition capable of maintaining an excellent antifouling property over a long period of time and capable of forming an antifouling coating film that is less susceptible to coating film defects such as coating film peeling, blistering, and cracks. And a coated article such as a fishing net, a ship, a marine structure or a gulf structure having a coating film of the antifouling coating composition.

  The present inventors have intensively studied to achieve the above object, and have obtained a polyester resin (A) having a specific structural unit in the resin skeleton, a silyl ester group-containing resin (B1) and / or a metal carboxylate structure. The coating film obtained by the antifouling coating composition containing the resin (B2) having the antifouling agent (C) can control the dissolution rate of the coating film in the ocean, In addition to maintaining excellent antifouling properties and excellent physical properties of the coating film, when the antifouling coating composition is applied to the bottom of a ship, the coating film is peeled off while sailing or at anchorage. It was found that coating film defects such as blisters and cracks are less likely to occur. The present invention has been completed based on such findings.

The present invention provides an antifouling coating composition described in the following items, and a coated article having the coating film.
(Item 1) An antifouling paint composition comprising 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). The polyester resin (A) has a structural unit represented by the following formula (1) in the resin skeleton, and the total mass of the structural units is 2 to 50 based on the mass of the polyester resin (A). It is a polyester resin in the range of mass%, and the mass ratio of the polyester resin (A) to the sum of the silyl ester group-containing resin (B1) and the resin having a metal carboxylate structure (B2) is 3 / The antifouling paint composition is within a range of 97 to 80/20.

（式中、Ｒ_０は水素原子又はメチル基を表し、ｍは１〜１００の整数を表す。）

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

(Item 2) The silyl ester group-containing resin (B1) is one or more of the monomers (b1) represented by the following formula (2) and a single amount other than the monomer (b1) Item 2. The antifouling paint composition according to Item 1, which is a copolymer with one or more of the bodies (b2).

［式中、Ｒ_４は水素原子又はメチル基を表し、Ｒ_１、Ｒ_２及びＲ_３はそれぞれ独立に炭化水素基を表し、Ｒ_５は水素原子又はＲ_６−Ｏ−ＣＯ−（ただし、Ｒ_６は有機基又は−ＳｉＲ_７Ｒ_８Ｒ_９で表されるシリル基を表し、Ｒ_７、Ｒ_８及びＲ_９はそれぞれ独立に炭化水素基を表す。）を表す。］

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

(Item 3) The resin (B2) having the metal carboxylate structure has a characteristic group having a metal carboxylate structure represented by the following formula (3), and has the metal carboxylate structure ( Item 2 or 2 characterized in that the content of metal atoms contained in B2) is in the range of 0.04 to 3.50 mol / Kg based on the solid content mass of the resin (B2). The antifouling paint composition as described.

（式中、Ｍは２価の金属原子を表し、Ｘは水酸基、有機酸残基及びアルコール残基からなる群より選ばれる少なくとも1種の基を表す。）

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

(Item 4) The polyester resin (A) is selected from the group consisting of raw material mixture containing at least one component selected from the group consisting of lactic acid, lactide of lactic acid and polylactic acid, and the group consisting of glycolic acid, glycolide and polyglycolic acid A polyester resin produced using at least one raw material mixture of the raw material mixture containing at least one component, and the acid value of the polyester resin (A) is in the range of 0.1 to 120 KOHmg / g. Item 5. The antifouling paint composition according to any one of Items 1 to 3, wherein
(Item 5) The antifouling paint composition according to any one of Items 1 to 4, wherein the polyester resin (A) has a weight average molecular weight in the range of 190 to 15000.
(Item 6) The antifouling paint composition according to any one of Items 1 to 5, wherein the polyester resin (A) does not have a metal carboxylate structure.
(Item 7) A coated article having a coating film of the antifouling paint composition according to any one of Items 1 to 6.

  The antifouling coating composition of the present invention is capable of maintaining excellent antifouling properties over a long period of time and forms a coating film in which coating film defects such as coating film peeling, blistering, and cracks are unlikely to occur. Can do.

  The antifouling coating composition of the present invention 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). It is a soil coating composition, Comprising: The said polyester resin (A) has the structural unit represented by following formula (1) in this resin frame | skeleton, and the total mass of the said structural unit is the mass of the said polyester resin (A). And a total of the polyester resin (A), the silyl ester group-containing resin (B1), and the resin having the metal carboxylate structure (B2). The mass ratio is in the range of 3/97 to 80/20.

（式中、Ｒ_０は水素原子又はメチル基を表し、ｍは１〜１００の整数を表す。）

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

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

[Polyester resin (A)]
The polyester resin (A) used in the antifouling coating composition of the present invention has a structural unit represented by the formula (1) in the resin skeleton. In order to introduce the structural unit represented by the formula (1) into the polyester resin, in the production of the resin, at least one component selected from the group consisting of lactic acid, lactide of lactic acid and polylactic acid, and glycolic acid and glycolide And at least one of at least one component selected from the group consisting of polyglycolic acid is preferably used as a raw material. In addition, the alias of glycolide in this specification is 1,4-dioxane-2,5-dione (1,4-Dioxane-2,5-dione).
Moreover, the total mass of the structural unit represented by the formula (1) is 2 to 50 mass% based on the mass of the polyester resin (A) when R ₀ in the formula (1) is a methyl group. In the case where R ₀ in the formula (1) is a hydrogen atom, preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the mass of the polyester resin (A), It is 2-50 mass%, Preferably it is 4-40 mass%, More preferably, it exists in the range of 6-30 mass%. When the total mass of the structural units 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 time.

The polyester resin (A) may be produced by a conventionally known method, and includes at least one component selected from the group consisting of lactic acid, lactic acid lactide and polylactic acid, and a group consisting of glycolic acid, glycolide and polyglycolic acid At least one component selected from at least one selected from the group consisting of lactic acid, lactic acid lactide and polylactic acid, and an acid component (a1) other than glycolic acid, glycolide and polyglycolic acid, lactic acid, lactic acid lactide and polylactic acid, and It can be produced by using alcohol components (a2) other than glycolic acid, glycolide and polyglycolic acid and reacting these components with each other.
The reaction for producing the polyester resin (A) includes any of known reactions such as esterification reaction, transesterification reaction, ring-opening polymerization reaction, and ring-opening addition reaction. Moreover, in this specification, the said reaction for manufacturing a polyester resin (A) may be called a "polymerization reaction."

In the production of lactic acid, lactic acid lactide and polylactic acid polyester resin (A), commercially available lactic acid, lactic acid lactide and polylactic acid may be used as they are. These compounds have optical isomers, respectively, but in the present invention, those containing L-form and D-form in an arbitrary ratio can be used. Manufacture of polyester resin (A) to form an antifouling coating film that can maintain excellent antifouling properties over a long period of time and is less likely to cause coating film defects such as coating film peeling, blistering, and cracks Among these compounds, it is particularly preferable to use lactate of lactic acid and / or polylactic acid among the above compounds.

In the production of glycolic acid, glycolide and polyglycolic acid polyester resin (A), commercially available products may be used as they are for glycolic acid, glycolide and polyglycolic acid. Manufacture of polyester resin (A) to form an antifouling coating film that can maintain excellent antifouling properties over a long period of time and is less likely to cause coating film defects such as coating film peeling, blistering, and cracks Among these compounds, it is particularly preferable to use glycolic acid and / or glycolide among the above compounds.

  Moreover, in manufacture of a polyester resin (A), the above-mentioned polylactic acid and polyglycolic acid can use the thing in the range whose weight average molecular weight is 450-1 million, respectively.

Acid component (a1)
In this invention, the acid component (a1) can use the acid component normally used for manufacture of a polyester resin. Examples of such acid components include alicyclic polybasic acids, aliphatic polybasic acids, aromatic polybasic acids, aromatic monocarboxylic acids, aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and these Examples include esterified products, anhydrides, and halides.

  Generally, an alicyclic polybasic acid is a compound having one or more alicyclic structures (mainly 4 to 6 membered rings) and two or more carboxyl groups in one molecule, and an acid anhydride of the compound, And esterified products and halides. Examples of the alicyclic polybasic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid, and 3-cyclohexene. -1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, tetrahydromethylphthalic acid, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, 1, Alicyclic polycarboxylic acids such as 2,4-cyclohexanetricarboxylic acid and 1,3,5-cyclohexanetricarboxylic acid; anhydrides of these alicyclic polycarboxylic acids; lower alkyls of these alicyclic polycarboxylic acids Examples include esterified products, which can be used alone or in combination of two or more. .

  The aliphatic polybasic acid is generally an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, and a halide of the aliphatic compound. Examples of the aliphatic polybasic acid include succinic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and brassle. And aliphatic polycarboxylic acids such as acids, octadecanedioic acid and citric acid; anhydrides of these aliphatic polyvalent carboxylic acids; halides of these aliphatic polyvalent carboxylic acids and the like. More than one species can be used in combination.

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

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

  Examples of the aromatic polybasic acid having three or more carboxyl groups in one molecule include trivalent aromatic polyvalent carboxylic acids and tetravalent aromatic polyvalent carboxylic acids. Examples of the trivalent aromatic polyvalent carboxylic acid include trimellitic acids such as trimellitic acid, trimellitic anhydride, trimellitic acid alkyl ester, trimellitic acid halide; hemimertic acid, hemimellitic anhydride, hemi Hemimellitic acids such as alkyl melicates and halides of hemimellitic acid; trimesic acids such as trimesic acid, trimesic acid alkyl esters and trimesic acid halides; various naphthalene tricarboxylic acids having different bonding positions of carboxyl groups to aromatic rings and their Anhydrous; various anthractricarboxylic acids with different bonding positions of carboxyl groups to aromatic rings and their anhydrides; various biphenyltricarboxylic acids with different bonding positions of carboxyl groups to aromatic rings and anhydrides; carboxyl groups to aromatic rings Bonding position is different Seed benzophenone tricarboxylic acid and anhydrides thereof; ethylene bis trimellitic acid and its anhydride. Examples of the tetravalent aromatic polyvalent carboxylic acid include pyromellitic acids such as pyromellitic acid, pyromellitic dianhydride, pyromellitic acid alkyl ester, and pyromellitic halide; Examples thereof include melophanoic acids such as anhydrides, alkyl esters of merophanic acid, and melophanic acid halides; planitic acids such as prehnitic acid, prenic acid anhydride, alkyl esters of prenic acid, and prenic acid halides. The said aromatic polybasic acid can be used individually or in combination of 2 or more types.

  In the present invention, the acid component (a1) used in the production of the polyester resin (A) may be a monocarboxylic acid such as an aromatic monocarboxylic acid, an aliphatic monocarboxylic acid, or an alicyclic monocarboxylic acid. . Examples of the aromatic monocarboxylic acid include benzoic acid, methylbenzoic acid, ethylbenzoic acid, pt-butylbenzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, and phenoxyacetic acid. And biphenyl carboxylic acid. Examples of the aliphatic monocarboxylic acid include acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, oleic acid, elaidic acid, brassic 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 Saturated or unsaturated aliphatic monocarboxylic acids such as tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, etc., are used alone or in combination of two or more can do.

  Examples of the alicyclic monocarboxylic acid include cyclohexanecarboxylic acid, cyclopentanecarboxylic acid, cycloheptanecarboxylic acid, 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, and 4-laurylcyclohexanecarboxylic acid. These can be used alone or in combination of two 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 the glycerin ester of the monocarboxylic acid. Examples of glycerin esters of monocarboxylic acids 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. Can be mentioned.

  Moreover, in this invention, it is preferable that the acid component (a1) used for manufacture of a polyester resin (A) contains an aromatic polybasic acid from a viewpoint of antifouling property long-term maintenance, The content is acid. Based on the total number of moles of component (a1), it is at least 30 mol%, preferably at least 50 mol%, more preferably at least 70 mol%.

Alcohol component (a2)
In this invention, the alcohol component (a2) can use the alcohol component normally used for manufacture of a polyester resin. As such an alcohol component, those containing dihydric alcohols such as alicyclic diols, aliphatic diols, aromatic diols and / or trihydric or higher polyhydric alcohols are preferable, for example, ethylene glycol, diethylene glycol, Triethylene glycol, tetraethylene glycol, pentaethylene glycol, 1,2-propylene glycol, di-1,2-propylene glycol, tri-1,2-propylene glycol, 1,2-butylene glycol, 2, 3-butylene glycol, 1,2-hexanediol, 1,2-dihydroxycyclohexane, 3-ethoxypropane-1,2-diol, 3-phenoxypropane-1,2-diol, neopentyl glycol, 2-methyl -1,3-propanediol, 2-methyl-2,4-pe Tandiol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentane Diol, 2-butyl-2-ethyl-1,3-propanediol, 2-phenoxypropane-1,3-diol, 2-methyl-2-phenylpropane-1,3-diol, 1,3-propylene glycol, 1,3-butylene glycol, 2-ethyl-1,3-octanediol, 1,3-dihydroxycyclohexane, 1,4-butanediol, 1,4-dihydroxycyclohexane, 1,5-pentanediol, 1,6- Hexanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,4-dimethylolcyclohexyl , Tricyclodecane dimethanol, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate (esterified product of hydroxypivalic acid and neopentyl glycol), bisphenol A, bisphenol F , Alkylene oxide adduct of bisphenol A, bis (4-hydroxyhexyl) -2,2-propane, bis (4-hydroxyhexyl) methane, 3,9-bis (1,1-dimethyl-2-hydroxyethyl)- Ester diol compounds such as 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (hydroxyethyl) terephthalate, glycerin, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, Dipentaerythritol, sorbite , Knit, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris (2-hydroxyethyl) isocyanurate, polylactone polyol compounds obtained by adding lactone compounds such as ε-caprolactone to these polyhydric alcohols, etc. These may be used alone or in combination of two or more.

  In addition, as required, methanol, ethanol, propyl alcohol, n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, stearyl Mono-alcohol compounds such as alcohol, 2-phenoxyethanol, dodecyl alcohol; mono-epoxy compounds such as ethylene oxide, propylene oxide, butylene oxide, glycidyl esters of synthetic hyperbranched saturated fatty acids (trade name “Cardura E10” manufactured by HEXION Specialty Chemicals) and protons Alcohol compounds obtained by reacting with acid-containing compounds are also used as auxiliary materials in the production of polyester resin (A) can do.

  In the present invention, the method for producing the polyester resin (A) is not particularly limited, and can be performed according to a known method. The polyester resin (A) is, for example, at least one component selected from the group consisting of lactic acid, lactic acid lactide and polylactic acid, and at least one component selected from the group consisting of glycolic acid, glycolide and polyglycolic acid. Polymerization of one component, one or more of the acid component (a1) and one or more of the alcohol component (a2) in a nitrogen stream at a temperature of 150 to 250 ° C. for 2 to 10 hours It can be made to react. In the above polymerization reaction, the reaction order of the raw materials may be arbitrarily adjusted, for example, after polylactic acid is obtained by ring-opening polymerization reaction of lactide of lactic acid in advance, or by ring-opening polymerization reaction of glycolide in advance. After obtaining the acid, 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) can also be obtained by a polymerization reaction and / or transesterification reaction between the polyester resin obtained by the polymerization reaction of the acid component (a1) and the alcohol component (a2) and lactide or glycolide of lactic acid. Can be obtained. These reactions may be performed in the presence of a known organic solvent.

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

In the present invention, the polyester resin (A) comprises at least one component selected from lactic acid, lactic acid lactide and polylactic acid, and at least one component selected from the group consisting of glycolic acid, glycolide and polyglycolic acid. Manufactured by a polymerization reaction of at least one component, an acid component (a1), and an alcohol component (a2), and if necessary, known organics other than the acid component (a1) and the alcohol component (a2) A compound and / or an inorganic compound may be contained as a constituent component, and the compound may be produced with a known chemical reaction such as an amidation reaction, a urethanization reaction, an imidation reaction, a carbonate reaction, or a urea reaction. For example, the polyester resin (A) can be used as a reaction intermediate or reaction product as an organic acid zinc, an organic acid copper, a zinc chloride, a copper chloride, a zinc hydroxide, a copper hydroxide, a zinc oxide during or after the polymerization reaction. Modified by reacting with metal compounds such as copper oxide, fatty acids, fats and oils, mono- or polyisocyanate compounds, mono- or polyamine compounds having nitrogen to which hydrogen atoms are bonded, epoxy compounds, acrylic resins, vinyl ester resins, etc. Polyester resin may be used. When the polyester resin (A) uses at least one component selected from the group consisting of glycolic acid, glycolide and polyglycolic acid as a raw material, organic compounds such as lactic acid, lactide of lactic acid and polylactic acid Can also be included as a constituent component other than the acid component (a1) and the alcohol component (a2).

  In addition, although the polyester resin (A) in this invention may have a metal carboxylate structure, in that case, it is contained in the said metal carboxylate structure on the basis of the solid content mass of the said polyester resin (A). The metal atom content is lower than the metal atom content contained in the resin (B2) having a metal carboxylate structure, which will be described later, and preferably less than 0.04 mol / Kg. It is more preferable that (A) does not substantially have the metal carboxylate structure. When the polyester resin (A) has a metal carboxylate structure, the production cost of the antifouling coating composition using the resin may increase.

  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, etc.), at the time of production or storage of the antifouling paint composition, The polyester resin (A) substantially not having a rate structure may react with a component containing the above-described metal compound to produce a metal carboxylate structure over time. The content of metal atoms contained in the metal carboxylate structure thus produced is 1.5 mol based on the solid content mass of the polyester resin (A) from the viewpoint of storage stability of the antifouling coating composition. It is preferably less than / Kg, more preferably in the range of less than 0.04 mol / Kg.

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

  Further, the resin acid value of the polyester resin (A) is preferably in the range of 0.1 to 120 mgKOH / g, from the viewpoint of maintaining the antifouling property of the obtained coating film over a long period of time. It is more preferably within the range of 1 to 95 mgKOH / g, and particularly preferably within the range of 0.3 to 50 mgKOH / g.

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

  In the present specification, the weight average molecular weight is a value obtained by converting the weight average molecular weight measured with a gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) based on the weight average molecular weight of polystyrene. The weight average molecular weight was determined by four columns (trade names: “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, and “TSKgel G-2000H × L” (any Can also be performed under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.

[Silyl ester group-containing resin (B1)]
The antifouling coating composition of the present invention further contains a silyl ester group-containing resin (B1) and / or a resin (B2) having a metal carboxylate structure in addition to the polyester resin (A). The silyl ester group-containing resin (B1) is a monomer (b1) having a polymerizable unsaturated group and a triorganosilyl ester group represented by the following general formula (2) (hereinafter referred to as “monomer ( b1) ”)) and one or more monomers (b2) having a polymerizable unsaturated group other than the monomer (b1). A copolymer, preferably a copolymer having a weight average molecular weight (Mw) in the range of 1000 to 150,000, and more preferably a copolymer having a Mw in the range of 3000 to 80000.

［式（２）中、Ｒ_４は水素原子又はメチル基を表し、Ｒ_１、Ｒ_２及びＲ_３はそれぞれ独立に炭化水素基を表し、Ｒ_５は水素原子又はＲ_６−Ｏ−ＣＯ−（ただし、Ｒ_６は有機基又は−ＳｉＲ_７Ｒ_８Ｒ_９で表されるシリル基を表し、Ｒ_７、Ｒ_８及びＲ_９はそれぞれ独立に炭化水素基を表す。）を表す。］

[In Formula (2), R ₄ represents a hydrogen atom or a methyl group, R ₁ , R ₂ and R ₃ each independently represents a hydrocarbon group, and R ₅ represents a hydrogen atom or R ₆ —O—CO— ( R ₆ represents an organic group or a silyl group represented by —SiR ₇ R ₈ R ₉ , and R ₇ , R ₈ and R ₉ each independently represent a hydrocarbon group. ]

  When the Mw of the silyl ester group-containing resin (B1) used in the antifouling coating composition of the present invention is less than 1000, the dissolution rate of the coating film obtained from the antifouling coating composition increases, but the physical properties of the coating film In some cases, coating film defects such as blisters and cracks are likely to occur. Moreover, when Mw of the said silyl ester group containing resin (B1) exceeds 150,000, the melt | dissolution rate of the coating film obtained from an antifouling coating composition will become slow, and it may be inferior to antifouling property.

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

Incidentally, _{R 4,} R 1, _{R 2} and _{R 3} in the formula (2-1) is the same as _{R 4,} R 1, _{R 2} and _{R 3} of each of the formulas (2).

The hydrocarbon group in R ₁ , R ₂ and R ₃ in the formula (2) or the formula (2-1) is a linear or branched alkyl group having 1 to 10 carbon atoms, or any Are preferably substituted or unsubstituted phenyl groups, and each hydrocarbon group may be the same or different. Among these, the hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, and in particular, a methyl group, an ethyl group, a propyl group, an n-butyl group, an s-butyl group, a t-butyl group, and an isopropyl group. An alkyl group such as a group is preferred.

  Examples of the monomer represented by the formula (2-1) (hereinafter referred to as “monomer (b1-1)”) include, for example, trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, Examples include trialkylsilyl (meth) acrylates such as triisopropylsilyl (meth) acrylate, and among these, solubility of the resulting coating film, durability of antifouling performance, difficulty in generating blisters and cracks In view of the above, triisopropylsilyl (meth) acrylate is preferred.

In the monomer (b1), R ₅ in the formula (2) is “R ₆ —O—CO—” (where R ₆ is an organic group or a silyl group represented by —SiR ₇ R ₈ R _9). And R ₇ , R ₈ and R ₉ each independently represents a hydrocarbon group.), It is represented by the following general formula (2-2).

Incidentally, _{R 4,} R 1, _{R 2} and _{R 3} in the formula (2-2) is the same as _{R 4,} R 1, _{R 2} and _{R 3} of each of the formulas (2).

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

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

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

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

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

  In addition, said alkyl group, a cycloalkyl group, an unsaturated alkyl group, and an aralkyl group may have a substituent. Examples of such a substituent include an alkoxy group and an acyl group. Further, 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 hindered.

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

The hydrocarbon group in R ₇ , R ₈ and R ₉ in the formula (2) or the formula (2-2) is a linear or branched alkyl group having 1 to 10 carbon atoms, or any Are preferably substituted or unsubstituted phenyl groups, and each hydrocarbon group may be the same or different. Among them, the hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, and in particular, a methyl group, an ethyl group, a propyl group, an n-butyl group, a s-butyl group, a t-butyl group, an isopropyl group, and the like. Alkyl groups are preferred.

  The monomer (b1) is preferably an isopropylsilyl group-containing unsaturated monomer from the viewpoints of solubility of the resulting coating film, durability of antifouling performance, difficulty in generating blisters and cracks, and the like. Examples of such an isopropylsilyl group-containing unsaturated monomer include triisopropylsilyl (meth) acrylate, triisopropylsilyl 4-pentenoate, bis (triisopropylsilyl) maleate, methyltriisopropylsilyl maleate, Ethyl triisopropylsilyl maleate, n-butyltriisopropylsilyl maleate, isobutyltriisopropylsilyl maleate, t-butyltriisopropylsilyl maleate, n-pentyltriisopropylsilyl maleate, isopentyltriisopropylsilyl maleate, malee 2-ethylhexyl triisopropylsilyl acid, cyclohexyl triisopropylsilyl maleate, bis (triisopropylsilyl) fumarate, methyltriisopropylsilyl fumarate Ethyl triisopropylsilyl fumarate, n-butyltriisopropylsilyl fumarate, isobutyltriisopropylsilyl fumarate, n-pentyltriisopropylsilyl fumarate, isopentyltriisopropylsilyl fumarate, 2-ethylhexyltriisopropylsilyl fumarate, fumarate Examples thereof include cyclohexyl triisopropylsilyl acid, and among these, triisopropylsilyl (meth) acrylate is particularly preferable. These triisopropylsilyl group-containing monomers can be used alone or in combination of two or more.

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

  When the mass ratio (b1) / (b2) of the monomer (b1) and the monomer (b2) is smaller than 20/80, the dissolution rate of the resulting coating film is slow, and the antifouling performance may be inferior. Yes, when the mass ratio (b1) / (b2) is greater than 70/30, the solubility of the resulting coating film is increased, but it is difficult to maintain the antifouling effect over a long period of time. Sometimes.

Examples of the monomer (b2) that can be copolymerized with the monomer (b1) (or the monomer (b1-1) and / or (b1-2)) include, for example, methyl (meth) acrylate, (meta ) Ethyl acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate ( (Meth) alkyl acrylates; (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-methoxypropyl, (meth) acrylic acid 4-methoxybutyl, (meth) acrylic acid 2-ethoxyethyl, etc. ) Alkoxyalkyl acrylates; ethylene glycol monomethyl (meth) acrylate, (meth) acrylates having polyoxyethylene chains with one molecular end being an alkoxy group Relate, (meth) acrylate having a polyoxypropylene chain whose molecular end is an alkoxy group, (meth) acrylic acid alkylene glycol monomethyl such as propylene glycol monomethyl (meth) acrylate; (meth) acrylic acid 2-hydroxy Ethyl, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, a monoesterified product of (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms, modified ε-caprolactone, allyl (Meth) acrylic acid hydroxyalkyls such as alcohols and hydroxyl-containing monomers such as (meth) acrylates having a polyoxyethylene chain whose molecular ends are hydroxyl groups; (meth) acrylonitrile, (meth) acrylamide, N, N-dimethyl (meta) ) Acrylamide, (meta ) Acryloylmorpholine, N-isopropyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) ) Nitrogen-containing monomers such as acrylates, N, N-dimethylaminopropyl (meth) acrylamide, adducts of glycidyl (meth) acrylate and amines; (meta) such as benzyl (meth) acrylate and phenyl (meth) acrylate ) Acrylic acid esters; Vinyl chloride; Vinylidene chloride; (Meth) acrylonitrile; Vinyl acetate; Butyl vinyl ether; Lauryl vinyl ether; N-vinyl pyrrolidone; Styrene; Vinyl toluene; That.
Examples of the monomer (b2) include vinyl ester compounds such as vinyl propionate and vinyl acetate; (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and croton. Carboxyl group-containing monomers such as acid and (meth) acrylic acid β-carboxyethyl; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxy Epoxy group-containing monomers such as cyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether; 2- (meth) acrylamide-2-methylpropanesulfonic acid, allylsulfonic acid, styrenesulfonic acid , Sul Sulfonic acid group-containing monomers such as foethyl (meth) acrylate and sodium salts or ammonium salts thereof; monomers having a phosphoric acid group such as 2- (meth) acryloyloxyethyl acid phosphate; acrolein, diacetone (meth) acrylamide, aceto Carbonyl group-containing monomers such as acetoxyethyl (meth) acrylate and vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) can also be used.

  The monomer (b2) exemplified above can be used alone or in combination of two or more. Among the monomers (b2) exemplified above, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( Preference is given to 2-methoxyethyl (meth) acrylate and 2-methoxypropyl (meth) acrylate.

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

  In the present invention, the silyl ester group-containing resin (B1) can be produced by a known polymerization method. The silyl ester group-containing resin (B1) may be any type of copolymer as long as it is a known copolymer such as a random copolymer, a graft copolymer, a gradient structure copolymer, or a block copolymer. It may be a coalescence.

  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 above copolymerization reaction include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile, and dimethyl-2. Azo compounds such as 2,2'-azobisisobutyrate; diacyl peroxide compounds such as dibenzoyl peroxide, di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dilauryl peroxide T-butyl peroxide compounds such as di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroctoate; t-amylperoxy-2-ethyl Hexanoate, t-amyl peroxyacetate, t-a T-amyl peroxide compounds such as ruperoxy isononanoate, t-amyl peroxybenzoate, t-amyl peroxyacetate, di (t-amyl peroxide), 1,1-di (t-amylperoxy) cyclohexane Class: t-hexyl peroxy-2-ethylhexanoate, t-hexyl peroxybenzoate, t-hexyl peroxy-isopropyl monocarbonate, t-hexyl peroxypivalate, t-hexyl peroxyneodecanoate, etc. And t-hexyl peroxide compounds. These polymerization initiators can be used alone or in combination of two or more.

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

  Examples of the polymerization method for obtaining the silyl ester group-containing resin (B1) include a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, and a suspension polymerization method. Among these, the solution polymerization method is particularly preferable because 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. Solvents; alcohol solvents such as isopropyl alcohol and butyl alcohol; ether solvents such as dioxane, 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. Moreover, these solvents can be used individually or in combination of 2 or more types.

  What is necessary is just to set the reaction temperature in the said copolymerization reaction suitably according to the kind etc. of a polymerization initiator, Usually, it is the temperature within the range of 70 to 160 degreeC, Preferably it is the temperature within the range of 80 to 140 degreeC. is there. Furthermore, what is necessary is just to set the reaction time in the said copolymerization reaction suitably according to reaction temperature, the kind of polymerization initiator, etc., and it is about 4 to 8 hours normally. The copolymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen gas or argon gas.

[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), the antifouling paint composition of the present invention is a resin (B2) having a metal carboxylate structure (this specification) In the description, the “resin (B2) having a metal carboxylate structure” may be simply referred to as “resin (B2)”. As the resin (B2), any resin having a metal carboxylate structure can be used without being limited by the type and composition of the resin.

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

（式中、Ｍは２価の金属原子を表し、Ｘは水酸基、有機酸残基及びアルコール残基からなる群より選ばれる少なくとも１種の基を表す。）

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

  Examples of the divalent metal atom M in the formula (3) include metal atoms such as zinc, copper, magnesium, calcium, iron and tellurium, preferably zinc or 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 includes, for example, a known resin having a carboxyl group and 1 mol of the carboxyl group in the resin. On the other hand, it can be obtained by reacting a divalent metal oxide or hydroxide in an amount in the range of 0.1 to 1.0 mol in the presence of water. The amount of water used in this reaction is preferably in the range of 0.1 to 10.0 mol with respect to 1 mol of the carboxyl group. If the amount of water used is less than 0.1 mol, the structural viscosity increases, and it may be difficult to handle the resin (B2) having a metal carboxylate structure. On the other hand, if the amount of water used exceeds 10.0 mol, an excessive water separation operation may be required.

  As a specific method for producing the resin (B2) containing the characteristic group (bb1), for example, a resin having a carboxyl group, water, and a divalent metal compound are put in a reaction vessel, The method of making it react for 1 to 20 hours at the temperature of 150 degreeC etc. is mentioned. The reaction may be performed 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 can be used alone or in combination of two or more.

  As the divalent metal compound used for the production of the resin (B2) containing the characteristic group (bb1), known ones can be used without particular limitation, but costs, toxicity, reactivity, etc. From the above, an oxide, salt or hydroxide of at least one metal selected from the group consisting of copper, zinc, calcium, magnesium, iron and tellurium is preferable, and an oxide, salt or hydroxide of zinc or copper is more preferable. preferable.

  Moreover, as resin which has the said carboxyl group used for manufacture of the said resin (B2) containing the said characteristic group (bb1), it is using resin, such as a vinyl polymer, polyester, a polyurethane, and a natural resin, for example. Yes, but with a large degree of freedom in changing the composition, carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, (meth) acrylic acid alkyl esters, styrene, etc. Vinyl polymers obtained by copolymerizing with other unsaturated monomers can be suitably used.

  Moreover, as resin (B2) containing the characteristic group (bb2) which has the metal carboxylate structure whose X in said Formula (3) is an organic acid residue, for example, the unsaturated monomer containing a characteristic group (bb2) (Bb2m) polymer or two or more kinds of copolymers, one or more unsaturated monomers (bb2m) containing the characteristic group (bb2) and other unsaturated monomers (bb2m) Examples thereof include a copolymer of one or more of the saturated monomers (m1), a resin obtained by modifying the copolymer by any method, and an arbitrary resin modified by the copolymer.

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

In said formula (4) or formula (5), R < ₁₀ >, R < ₁₁ > and R < ₁₂ > represent a hydrogen atom or a methyl group, A represents an organic acid residue, and M represents a bivalent 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 polymerizable unsaturated compounds such as (meth) acrylic acid. A method of reacting an organic acid with a metal compound such as an oxide, hydroxide, or salt of a divalent metal and a monobasic organic acid capable of forming an organic acid residue, a polymerizable unsaturated organic acid, Examples include a method of reacting with a metal salt of a basic organic acid. These reactions may be performed in the presence of an organic solvent and / or water as necessary.

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

  When X in the formula (3) is an organic acid residue, examples of the organic acid residue include acetic acid, monochloroacetic acid, monofluoroacetic acid, naphthenic acid, propionic acid, caproic acid, caprylic acid, and 2-ethylhexylic acid. , Capric acid, versatic acid, isostearic acid, palmitic acid, crestic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, stearolic acid, ricinoleic acid, ricinoelaidic acid, brassic acid, erucic acid, α-naphthoic acid , Β-naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinolinecarboxylic acid, nitrobenzoic acid, nitronaphthalenecarboxylic acid, puruvic acid, abietic acid, neoabietic acid, Dehydroabietic acid, hydrogenated abietic acid, parastronic acid, pimaric acid, Examples thereof include those derived from organic acids such as isopimaric acid, levopimaric acid, dextropimaric acid, sandaracopimalic acid, resin acid, abietane, pimaran, isopimaran, and compounds having a labdane skeleton. Moreover, what is induced | guided | derived from the said organic acid can also be mentioned about the organic acid residue represented by A in the said Formula (4).

  Specific examples of the unsaturated monomer (bb2m-1) include, for example, magnesium acetate (meth) acrylate, zinc acetate (meth) acrylate, zinc naphthenate (meth) acrylate, copper acetate (meth) acrylate, and naphthenic acid. Copper (meth) acrylate, monochloro magnesium acetate (meth) acrylate, monochloro zinc acetate (meth) acrylate, monochloro copper acetate (meth) acrylate, magnesium monofluoroacetate (meth) acrylate, zinc monofluoroacetate (meth) acrylate, monofluoro Copper acetate (meth) acrylate, magnesium propionate (meth) acrylate, zinc propionate (meth) acrylate, copper propionate (meth) acrylate, magnesium caproate (meth) acrylate, zinc caproate (meta Acrylate, copper caproate (meth) acrylate, magnesium caprylate (meth) acrylate, zinc caprylate (meth) acrylate, copper caprylate (meth) acrylate, magnesium 2-ethylhexylate (meth) acrylate, zinc 2-ethylhexylate ( (Meth) acrylate, copper 2-methylhexylate (meth) acrylate, magnesium caprate (meth) acrylate, zinc caprate (meth) acrylate, copper caprate (meth) acrylate, magnesium versatate (meth) acrylate, zinc versatate ( (Meth) acrylate, copper versatate (meth) acrylate, magnesium isostearate (meth) acrylate, zinc isostearate (meth) acrylate, copper isostearate (meth) Chlorate, magnesium palmitate (meth) acrylate, zinc palmitate (meth) acrylate, copper palmitate (meth) acrylate, magnesium cresomate (meth) acrylate, zinc cresotinate (meth) acrylate, copper cresotate (meth) acrylate, Magnesium oleate (meth) acrylate, zinc oleate (meth) acrylate, copper oleate (meth) acrylate, magnesium elaidate (meth) acrylate, zinc elaidate (meth) acrylate, copper elaidate (meth) acrylate, linoleic acid Magnesium (meth) acrylate, zinc linoleate (meth) acrylate, copper linoleate (meth) acrylate, magnesium linolenate (meth) acrylate, zinc linolenate (meth) Acrylate, copper linolenate (meth) acrylate, stearol magnesium (meth) acrylate, zinc stearolate (meth) acrylate, copper stearolate (meth) acrylate, magnesium ricinoleate (meth) acrylate, zinc ricinoleate (meth) Acrylate, copper ricinoleate (meth) acrylate, magnesium ricinoelaidate (meth) acrylate, zinc ricinoelaidate (meth) acrylate, copper ricinoelaidate (meth) acrylate, magnesium brassinate (meth) acrylate, brassic acid Zinc (meth) acrylate, brassic acid copper (meth) acrylate, magnesium erucate (meth) acrylate, zinc erucate (meth) acrylate, copper erucate (meth) acrylate, α-naphth Magnesium acrylate (meth) acrylate, α-naphthoic acid zinc (meth) acrylate, α-naphthoic acid copper (meth) acrylate, β-magnesium naphthoic acid (meth) acrylate, β-naphthoic acid zinc (meth) acrylate, β- Naphthoic acid copper (meth) acrylate, magnesium benzoate (meth) acrylate, zinc benzoate (meth) acrylate, copper benzoate (meth) acrylate, 2,4,5-trichlorophenoxy magnesium acetate (meth) acrylate, 2,4 , 5-trichlorophenoxyacetic acid zinc (meth) acrylate, 2,4,5-trichlorophenoxyacetic acid copper (meth) acrylate, 2,4-dichlorophenoxyacetic acid magnesium (meth) acrylate, 2,4-dichlorophenoxyacetic acid zinc (meta ) Acrylate, 2, 4 Copper dichlorophenoxyacetate (meth) acrylate, magnesium quinolinecarboxylate (meth) acrylate, zinc quinolinecarboxylate (meth) acrylate, copper quinolinecarboxylate (meth) acrylate, magnesium nitrobenzoate (meth) acrylate, zinc nitrobenzoate ( Meth) acrylate, copper nitrobenzoate (meth) acrylate, magnesium nitronaphthalenecarboxylate (meth) acrylate, zinc nitronaphthalenecarboxylate (meth) acrylate, copper nitronaphthalenecarboxylate (meth) acrylate, magnesium puruvate (meth) acrylate , Zinc puruvate (meth) acrylate, and copper (meth) acrylate puruvate. These unsaturated monomers (bb2m-1) can be used by appropriately selecting one type or two or more types as necessary.

Examples of the unsaturated monomer (bb2m-2) represented by the above formula (5) include magnesium acrylate ((CH ₂ ═CHCOO) ₂ Mg), magnesium methacrylate ((CH ₂ ═C (CH ₃ )). ) COO) ₂ Mg), zinc acrylate ((CH ₂ ═CHCOO) ₂ Zn), zinc methacrylate ((CH ₂ ═C (CH ₃ ) COO) ₂ Zn), copper acrylate ((CH ₂ ═CHCOO)) ₂ Cu), copper methacrylate ((CH ₂ ═C (CH ₃ ) COO) ₂ Cu), and the like. These unsaturated monomers (b2m-2) can be used by appropriately selecting one type or two or more types as necessary, and among these unsaturated monomers, the obtained coating film can be used. From the viewpoint of maintaining antifouling performance for a long period of time, it is preferable to use zinc (meth) acrylate.

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

  Moreover, the usage-amount of the said unsaturated monomer (bb2m-2) used for obtaining resin (B2) containing the said characteristic group (bb2) is a viewpoint which maintains the antifouling performance of the coating film obtained for a long period of time. From the solid content mass of the resin (B2), it is preferably in the range of 0.5 to 50.0 mass%, more preferably in the range of 1.0 to 30.0 mass%.

  As the resin (B2) containing the characteristic group (b3) having a metal carboxylate structure in which X in the above formula (3) is an alcohol residue, for example, an unsaturated monomer (b3m) containing the characteristic group (b3) Or two or more copolymers, one or more unsaturated monomers (b3m) containing a characteristic group (b3), and an unsaturated monomer other than the unsaturated monomer (b3m) Examples thereof include a copolymer of the body (m2) with one or more kinds, a resin obtained by modifying the copolymer by any method, and an arbitrary resin modified by the copolymer.

  Examples of the method for producing the unsaturated monomer (b3m) include polymerizable unsaturated organic acids such as (meth) acrylic acid and metal compounds such as divalent metal oxides, hydroxides and salts. And a method of reacting an alcohol capable of forming an alcohol residue, a method of reacting a polymerizable unsaturated organic acid and a metal alkoxide compound, and the like. These reactions may be performed in the presence of an organic solvent and / or water as necessary.

  Further, the resin (B2) includes at least one unsaturated monomer selected from the group consisting of the unsaturated monomers (bb2m-1), (bb2m-2), and (b3m), and as necessary. It can also be obtained by copolymerizing one or more 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 those exemplified as the monomer (b2) that can be used in the production of the silyl ester group-containing resin (B1). it can.

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

  The resin (B2) is, for example, a known resin having a carboxyl group and a divalent metal in an amount in the range of 0.1 to 1.0 mol with respect to 1 mol of the carboxyl group in the resin. It may be produced by reacting a metal compound such as an oxide or hydroxide with an organic acid, an alcohol compound, water, or the like, if necessary, at a temperature of 50 ° C. to 200 ° C. 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 this reaction is selected from the group consisting of a hydroxyl group, an organic acid residue, and an alcohol residue. The constituent ratio is not particularly limited as long as it is at least one kind of group. In addition, this reaction may be performed in the presence of a suitable organic solvent, and examples of the organic solvent in that case include alcohol-based, ketone-based, ester-based, and ether-based solvents. These can be used alone or in combination of two or more.

  As the divalent metal compound used for the production of the resin (B2), known compounds can be used without particular limitation, but zinc, copper, magnesium, calcium, etc. can be used from the viewpoints of cost, toxicity, reactivity, and the like. An oxide, salt or hydroxide of at least one metal selected from the group consisting of iron and tellurium is preferred, and an oxide, salt or hydroxide of zinc or copper is more preferred.

  The resin having the carboxyl group used for the production of the resin (B2) can be, for example, a resin such as a vinyl polymer, polyester, polyurethane, natural resin, etc. (Meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and other carboxyl group-containing unsaturated monomers and (meth) acrylic acid alkyl esters, styrene and other unsaturated monomers. A vinyl polymer obtained by polymerization can be preferably used.

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

  In the present invention, X in the characteristic group having a metal carboxylate structure represented by the general formula (3) contained in the resin having a metal carboxylate structure (B2) is a hydroxyl group, an organic acid residue, and an alcohol residue. What is necessary is just at least 1 sort (s) of groups chosen from the group which consists of, Furthermore, content of the metal atom contained in the said metal carboxylate structure is 0.04-3.3 on the basis of solid content mass of the said resin (B2). It is in the range of 50 mol / Kg, preferably in the range of 0.07 to 3.00 mol / Kg, more preferably in the range of 0.10 to 2.50 mol / Kg. When the content of the metal atom is more than 3.50 mol / Kg, the antifouling retention period of the resulting coating film may be shortened, and when it is less than 0.04 mol / Kg, the resulting coating is obtained. There is a tendency for the antifouling property of the membrane to decrease.

  Examples of other methods for producing the resin (B2) having a metal carboxylate structure include a condensation reaction between a compound having two or more carboxyl groups in one molecule and a metal compound, and a polyol compound having a metal carboxylate structure. Examples include the polyaddition reaction or the condensation reaction used.

[Anti-fouling agent (C)]
The antifouling paint composition of the present invention comprises an antifouling agent (C) in addition to the polyester resin (A), the silyl ester group-containing resin (B1) and / or the resin (B2) having a metal carboxylate structure. In addition. As the antifouling agent (C), conventionally known antifouling agents can be used, and examples thereof include inorganic compounds, organic compounds containing metals, and organic compounds not containing metals.

  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 sulfate, and copper-nickel alloy. And nickel compounds.

  As the organic compound containing the metal, for example, an organic copper-based compound, an organic nickel-based compound, an organic zinc-based compound, or the like can be used. In addition, manneb, manceb, propineb, or the like can also be used. Furthermore, examples of the organic copper compound include copper oxine, copper pyrithione, copper nonylphenol sulfonate, copper bis (ethylenediamine) -bis (dodecylbenzenesulfonate), copper acetate, copper naphthenate, and bis (pentachlorophenolic acid). Copper etc. are mentioned. Examples of the organic nickel compound include nickel acetate and nickel dimethyldithiocarbamate. Examples of the organic zinc compound include zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, zinc pyrithione, and zinc ethylenebisdithiocarbamate.

  Examples of the organic compound containing no metal include N-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino-1,3-thiazolidine-2,4-dione, dithiocyano compound, and triazine compound. Compounds and the like.

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

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

  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 And '-ethyl-6'-methylphenyl) maleimide.

  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-dimethylaminobenzylideneamino) -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, and 2,5-dithiocyanothiophene.

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

  In addition to the organic compounds exemplified above, examples of the organic compound containing no metal include 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, 4,5- Dichloro-2-N-octyl-3- (2H) isothiazolone, N, N-dimethyl-N′-phenyl- (N-fluorodichloromethylthio) sulfamide, tetramethylthiuram disulfide, 3-iodo-2-propynylbutylcarbamate, 2- (methoxycarbonylamino) benzimidazole, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, diiodomethylparatolylsulfone, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, phenyl (bispyridine) Bismuth dichloride, 2- 4-thiazolyl) benzimidazole, triphenylboronpyridine-amine complex, medetomidine (system name: (±) 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole), dichloro-N-(( Dimethylamino) sulfonyl) fluoro-N- (p-tolyl) methanesulfenamide, 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole, chloromethyl-n-octyl disulfide, etc. Is mentioned.

  The said antifouling agent (C) can use each compound illustrated above individually or in combination of 2 or more types. The antifouling agent (C) is preferably cuprous oxide from the viewpoint of exhibiting stable antifouling performance among the compounds exemplified above, and in particular, cuprous oxide and copper pyrithione are used in combination. It is preferable to do.

[Anti-fouling paint composition and coated article having the coating film]
The antifouling coating composition of the present invention 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). A stain coating composition, wherein the polyester resin (A) has a structural unit represented by the formula (1) in the resin skeleton, the polyester resin (A), and a silyl ester group-containing resin (B1). ) And the total of 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 (B2) having a metal carboxylate structure is in the range of 3/97 to 80/20, preferably Is in the range of 7/93 to 60/40, more preferably in the range of 10/90 to 40/60. When the mass ratio is in the range of 3/97 to 80/20, the antifouling performance of the antifouling coating film obtained by the antifouling coating composition of the present invention can be maintained over a long period of time. In addition, in the antifouling coating film, coating film defects such as coating film peeling, blistering, and cracking are less likely to occur. When the said mass ratio is smaller than 3/97 or larger than 80/20, it may become difficult to maintain the antifouling performance of the coating film obtained over a long period of time.

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

  In the antifouling coating composition of the present invention, the content of the antifouling agent (C) includes the polyester resin (A), a silyl ester group-containing resin (B1), and a resin (B2) having a metal carboxylate structure. Is in the range of 50 to 500 mass%, preferably in the range of 250 to 400 mass%. 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. When there is more content of C) than 500 mass%, the physical property of the coating film obtained will fall and malfunctions, such as peeling and a swelling, may generate | occur | produce.

  In addition to the polyester resin (A), the silyl ester group-containing resin (B1) and / or the resin (B2) having a metal carboxylate structure, and the antifouling agent (C), the antifouling coating composition of the present invention includes: Additives such as pigments, dyes, dehydrating agents, plasticizers, tarnishing agents (anti-sagging agents), antifoaming agents, antioxidants; polyester resins (A), silyl ester group-containing resins (B1), and metal carboxylate structures Various components used in general coating compositions such as a resin other than the resin (B2) having an organic acid, an organic acid, and a solvent can be blended as necessary. These components can be used alone or in combination of two or more.

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

  The content of the pigment in the antifouling coating composition of the present invention is 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). , 0.05 to 1000% by mass is preferable, and 1 to 500% by mass is more preferable.

  The dehydrating agent is a component that contributes to improving the storage stability of the antifouling coating composition. Examples of such dehydrating agents include inorganic gypsum, hemihydrate gypsum (calcined gypsum), synthetic zeolite-based adsorbents (for example, “Molecular Sieve” (trade name), etc.), etc. Orthoesters (for example, methyl orthoformate, methyl orthoacetate, orthoborate, etc.), silicates, isocyanates and the like can be mentioned. Among these, anhydrous gypsum and hemihydrate gypsum (calcined gypsum) which are inorganic dehydrating agents are preferable. Moreover, these dehydrating agents may be used individually by 1 type, and may use 2 or more types together. The content of the dehydrating agent in the antifouling coating composition can be appropriately adjusted, but the polyester resin (A), the silyl ester group-containing resin (B1), and the resin having a metal carboxylate structure (B2) Is preferably in the range of 0 to 100 mass%, more preferably in the range of 0.5 to 25 mass%.

  The plasticizer is a component that contributes to improving crack resistance and water resistance of the resulting antifouling coating film. Examples of such plasticizers include tricresyl phosphate, dioctyl phthalate, chlorinated paraffin, liquid paraffin, n-paraffin, chlorinated paraffin, polybutene, terpene phenol, tricresyl phosphate (TCP), and polyvinylethyl. Examples include ether. These plasticizers may be used alone or in combination of two or more. In addition, when mix | blending a plasticizer in the antifouling coating composition of this invention, content of the plasticizer in the said antifouling coating composition is polyester resin (A), silyl ester group containing resin (B1), and The total mass with the resin (B2) having a metal carboxylate structure is preferably in the range of 0.5 to 10% by mass, and more preferably in the range of 1 to 5% by mass.

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

  Examples of the alteration agent include organic waxes (for example, polyethylene wax, oxidized polyethylene wax, polyamide wax, amide wax, hydrogenated castor oil wax, etc.), organic clay compounds (for example, Al, Ca, Zn). Amine salts, stearate salts, lecithin salts, alkyl sulfonates, etc.), bentonite, synthetic fine silica and the like. These alteration agents may be used alone or in combination of two or more. In the case where the antifouling coating composition of the present invention is blended with a habit-changing agent, the content of the habit-changing agent in the anti-fouling coating composition can be appropriately adjusted. For example, the polyester resin (A) and The total mass of the silyl ester group-containing resin (B1) and the resin (B2) having a metal carboxylate structure is within the range of 0.25 to 50% by mass.

  In addition to the polyester resin (A), the silyl ester group-containing resin (B1), and the resin having a metal carboxylate structure (B2), the antifouling coating composition of the present invention includes one or more kinds as necessary. Other resins may be contained. Examples of such resins include acrylic resins, acrylic silicone resins, epoxy resins, fluororesins, polybutene resins, silicone rubbers, urethane resins, polyamide resins, and vinyl chlorides that are widely used as base resins for antifouling paints. Copolymer resins, chlorinated rubber, chlorinated olefin resins, styrene / butadiene copolymer resins, ketone resins, ethylene-vinyl acetate copolymer resins, vinyl chloride resins, alkyd resins, coumarone resins, terpene phenol resins, petroleum resins, etc. It is done.

  The antifouling coating composition of the present invention may contain a known rosin compound. Examples of such rosin compounds include rosin, rosin derivatives, rosin metal salts, and the like. Furthermore, examples of the rosin include tall rosin, gum rosin, and wood rosin. Examples of the rosin derivative include hydrogenated rosin, maleated rosin obtained by reacting rosin and maleic anhydride, formylated rosin, and polymerized rosin. Examples of the rosin metal salt include zinc chloride, calcium rosinate, copper rosinate, magnesium rosinate, and other reactants of a metal compound and rosin. These rosin compounds can be used alone or in combination of two or more.

  When a rosin compound is blended in the antifouling coating composition of the present invention, the content of the rosin compound in the antifouling coating composition is not particularly limited. For example, the polyester resin (A) and On the basis of the total mass of the silyl ester group-containing resin (B1) and the resin (B2) having a metal carboxylate structure, 50% by mass or less is preferable, and 30% by mass or less is more preferable.

  The antifouling coating composition of the present invention comprises an aliphatic solvent, an aromatic solvent (for example, xylene, toluene, etc.), a ketone solvent (for example, methyl isobutyl ketone, cyclohexanone, etc.), an ester solvent, an ether solvent (for example, An organic solvent generally used as a solvent for antifouling paints such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like, and alcohol solvents (for example, isopropyl alcohol and the like) can be blended. In addition, although the compounding quantity of the organic solvent can be appropriately adjusted, for example, the compounding quantity is such that the total solid content of the antifouling coating composition is in the range of 20 to 90% by mass. You may add further according to workability.

  The antifouling coating composition of the present invention can be prepared by the same method as known antifouling coating compositions. For example, a polyester resin (A), a silyl ester group-containing resin (B1) and / or a resin (B2) having a metal carboxylate structure, an antifouling agent (C), and, if necessary, the organic solvent or additive And the like can be added to the stirring tank at once or sequentially, and stirred and mixed.

  The coated article of the present invention is an article having a coating film of the antifouling coating composition of the present invention. The coated article includes a step of applying or impregnating the antifouling coating composition one or more times to the surface of a substrate, and a step of drying the applied or impregnated antifouling coating composition. Can be obtained.

  Examples of the base material include a base material that is in contact with seawater or fresh water (for example, constantly or intermittently), specifically, an underwater structure; a ship outer plate or a ship bottom; a water conduit or a cooling pipe of a power plant; Examples include aquaculture or stationary fishing nets, fishing gear, or floats used in them; fishing net accessories such as ropes. In addition, although the film thickness of the coating film obtained from the antifouling coating composition of the present invention can be appropriately adjusted in consideration of the consumption rate (dissolution rate) of the coating film, for example, the film per coating time The thickness (μm) may be 30 to 250 μm / times, preferably about 75 to 150 μm / time, and may be applied twice or more to about 60 to 500 μm as necessary.

  In obtaining the coated article, the surface of the substrate is coated with a primer, an anticorrosive coating, and optionally a binder coating, and the surface of the present invention is applied by means such as brush coating, spray coating, roller coating, or dipping. An antifouling paint composition may be applied. Further, the antifouling coating composition of the present invention may be overcoated on the surface of an existing antifouling coating film. The coating film can be dried at room temperature, but may be heat-dried at a temperature up to about 100 ° C. as necessary.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited only to an Example. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.

Production of polyester resin (A) (Production Example 1) Production of polyester resin (A1) In a 2 L reactor equipped with a thermometer, a stirrer and a rectifying tower, 415.3 parts of PA, 235.7 parts of NPG, 237.9 parts of DEG and 161.6 parts of lactic acid lactide were charged, and the temperature of the reactor contents was raised to 160 ° C. Next, the reactor temperature was raised from 160 ° C. to 230 ° C. over 3 hours, and the content temperature was maintained at 230 ° C. for 2 hours. Then, the rectification column was replaced with a water separator, and the reactor was About 50.0 parts of xylene was charged, and polycondensation proceeded while removing condensed water by azeotropically distilling water and xylene. After confirming that the acid value of the produced polyester resin is 3.0 mgKOH / g or less, heating is stopped, cooling is started, and xylene is added to dilute to obtain a polyester resin having a solid content of 70% ( A1) A solution was obtained. The acid value of the above-mentioned resin was measured by dissolving a measurement sample using a mixed solution of toluene and isopropanol (mass ratio 1/1) as a solvent and titrating an alcoholic solution of 1/10 N potassium hydroxide. .

Here, the relationship between the abbreviations of the polyester raw materials in the present specification and the corresponding compounds 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-hexane Diol, BEPG; 2-butyl-2-ethyl-1,3-propanediol, CHDM; 1,4-cyclohexanedimethanol, DEG; diethylene glycol, TEG; triethylene glycol, tetraEG; tetraethylene glycol, DPG; dipropylene Glycol, TMP; Trimethylolpropane, G; Glycerin, PE; Pentaerythritol, LA; Lactic acid lactate, GL; Glycolide

(Manufacture examples 2-8, 13-17) Manufacture of polyester resin (A2)-(A8), (A13)-(A17) The acid component and alcohol component in manufacture example 1 are shown in Table 1-1. Except having carried out, it carried out similarly to manufacture example 1, and obtained the resin solution of each polyester resin (A2)-(A8), (A13)-(A17) of 70% of solid content.

(Production Example 9) Production of polyester resin (A9) In a 2 L reactor equipped with a thermometer, a stirrer and a rectifying tower, 340.9 parts of iPA, 215.6 parts of NPG, 217.7 parts of DEG, 147.8 parts of lactide of lactic acid was charged, and the temperature of the reactor contents was raised to 160 ° C. Next, the reactor temperature was raised from 160 ° C. to 230 ° C. over 3 hours, and the content temperature was maintained at 230 ° C. for 2 hours. Then, the rectification column was replaced with a water separator, and the reactor was About 45 parts of xylene was charged, and polycondensation proceeded while removing condensed water by azeotropically distilling water and xylene. After confirming that the acid value of the produced polyester resin was 3.0 mgKOH / g or less, the content temperature was cooled to 160 ° C. Further, 152.0 parts of PA was added and maintained at 160 ° C. for 1 hour for addition reaction (half esterification), and then cooling was started. After cooling to 130 ° C., xylene was added and diluted to obtain a polyester resin (A9) resin solution having a solid content of 70%.

(Production Example 10) Production of polyester resin (A10) In a 2 L reactor equipped with a thermometer, a stirrer and a rectifying tower, 292.8 parts of iPA, 185.2 parts of NPG, 186.9 parts of DEG, 127.0 parts of lactic acid lactide was charged, and the temperature of the reactor contents was raised to 160 ° C. Next, the reactor temperature was raised from 160 ° C. to 230 ° C. over 3 hours, and the content temperature was maintained at 230 ° C. for 2 hours. Then, the rectification column was replaced with a water separator, and the reactor was About 45 parts of xylene was charged, and polycondensation proceeded while removing condensed water by azeotropically distilling water and xylene. After confirming that the acid value of the produced polyester resin was 3.0 mgKOH / g or less, the content temperature was cooled to 160 ° C. Further, 276.1 parts of HHPA was added and maintained at 160 ° C. for 1 hour for addition reaction (half-esterification), and then cooling was started. After cooling to 130 ° C., xylene was added and diluted to obtain a resin solution of a polyester resin (A10) having a solid content of 70%.

(Production Example 11) Production of polyester resin (A11) In a 2 L reactor equipped with a thermometer, a stirrer and a rectifying tower, 415.3 parts of PA, 235.7 parts of NPG, 237.9 parts of DEG, 229.5 parts of 88 mass% lactic acid aqueous solution was prepared, and the temperature of the content of the reactor was raised to 130 ° C. Next, the reactor temperature was raised from 130 ° C. to 160 ° C. over 3 hours, and the content temperature was maintained at 230 ° C. for 2 hours. Then, the rectification column was replaced with a water separator, and the reactor was About 50.0 parts of xylene was charged, and polycondensation proceeded while removing condensed water by azeotropically distilling water and xylene. After confirming that the acid value of the produced polyester resin is 3.0 mgKOH / g or less, heating is stopped, cooling is started, and xylene is added to dilute the polyester resin (A11 having a solid content of 70%). ) Resin solution was obtained.

(Production Example 12) Production of polyester resin (A12) In a 2 L reactor equipped with a thermometer, a stirrer and a water separator, 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 of lactic acid, and 50.0 parts of xylene were charged, and the reactor temperature was raised to 160 ° C. and held for 1 hour. Subsequently, the content temperature of the reactor was raised from 160 ° C. to 240 ° C. over 4 hours, and polycondensation proceeded at 240 ° C. while removing the produced condensed water. After confirming that the resin acid value is about 3.0 mgKOH / g or less, heating is stopped and cooling is started, and xylene is added to dilute the polyester resin (A12) having a solid content of 70%. A resin solution was obtained.

  The resin acid values and 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 blending amounts of the respective production examples.

(Production Example 1 ′) Production of Polyester Resin (A1 ′) In a 2 L reactor equipped with a thermometer, a stirrer and a rectifying tower, 428.7 parts of PA, 243.3 parts of NPG, 245.7 parts of DEG Part, glycolide (GL) 134.4 parts was charged, and the temperature of the content of the reactor was raised to 160 ° C. Next, the reactor temperature was raised from 160 ° C. to 230 ° C. over 3 hours, and the content temperature was maintained at 230 ° C. for 2 hours. Then, the rectification column was replaced with a water separator, and the reactor was About 50.0 parts of xylene was charged, and polycondensation proceeded while removing condensed water by azeotropically distilling water and xylene. After confirming that the acid value of the produced polyester resin is 3.0 mgKOH / g or less, heating is stopped, cooling is started, and xylene is added to dilute to obtain a polyester resin having a solid content of 70% ( A1 ′) A solution was obtained.

(Production Examples 2 ′ to 8 ′, 13 ′ to 18 ′) Production of Polyester Resins (A2 ′) to (A8 ′) and (A13 ′) to (A18 ′) The acid component and the alcohol component in Production Example 1 ′ were used. The polyester resins (A2 ′) to (A8 ′) and (A13 ′) to (A18 ′) having a solid content of 70% were prepared in the same manner as in Production Example 1 ′ except that the formulation shown in Table 1-2 was used. A resin solution was obtained.

(Production Example 9 ′) Production of polyester resin (A9 ′) In a 2 L reactor equipped with a thermometer, a stirrer, and a rectifying tower, 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 reactor contents was raised to 160 ° C. Next, the reactor temperature was raised from 160 ° C. to 230 ° C. over 3 hours, and the content temperature was maintained at 230 ° C. for 2 hours. Then, the rectification column was replaced with a water separator, and the reactor was About 45 parts of xylene was charged, and polycondensation proceeded while removing condensed water by azeotropically distilling water and xylene. After confirming that the acid value of the produced polyester resin was 3.0 mgKOH / g or less, the content temperature was cooled to 160 ° C. Further, 156.4 parts of PA was added and maintained at 160 ° C. for 1 hour for addition reaction (half esterification), and then cooling was started. After cooling to 130 ° C., xylene was added and diluted to obtain a resin solution of a polyester resin (A9 ′) having a solid content of 70%.

(Production Example 10 ′) Production of polyester resin (A10 ′) In a 2 L reactor equipped with a thermometer, a stirrer and a rectifying tower, 300.2 parts of iPA, 189.9 parts of NPG, 191.7 parts of DEG And 104.9 parts of glycolide were charged, and the temperature of the reactor contents was raised to 160 ° C. Next, the reactor temperature was raised from 160 ° C. to 230 ° C. over 3 hours, and the content temperature was maintained at 230 ° C. for 2 hours. Then, the rectification column was replaced with a water separator, and the reactor was About 45 parts of xylene was charged, and polycondensation proceeded while removing condensed water by azeotropically distilling water and xylene. After confirming that the acid value of the produced polyester resin was 3.0 mgKOH / g or less, the content temperature was cooled to 160 ° C. Further, 278.5 parts of HHPA was added and maintained at 160 ° C. for 1 hour for addition reaction (half-esterification), and then cooling was started. After cooling to 130 ° C., xylene was added and diluted to obtain a resin solution of a polyester resin (A10 ′) having a solid content of 70%.

(Production Example 11 ′) Production of Polyester Resin (A11 ′) In a 2 L reactor equipped with a thermometer, a stirrer and a rectifying tower, 428.7 parts of PA, 243.3 parts of NPG, 245.7 parts of DEG Part and 176.1 parts of glycolic acid were charged, and the temperature of the contents of the reactor was raised to 130 ° C. Next, the reactor temperature was raised from 130 ° C. to 160 ° C. over 3 hours, and the content temperature was maintained at 230 ° C. for 2 hours. Then, the rectification column was replaced with a water separator, and the reactor was About 50.0 parts of xylene was charged, and polycondensation proceeded while removing condensed water by azeotropically distilling water and xylene. After confirming that the acid value of the produced polyester resin is 3.0 mgKOH / g or less, heating is stopped, cooling is started, and xylene is added to dilute to obtain a polyester resin having a solid content of 70% ( A resin solution of A11 ′) was obtained.

Production Example 12 ′ Production of Polyester Resin (A12 ′) In a 2 L reactor equipped with a thermometer, a stirrer and a water separator, 217.4 parts of PA, 18.2 parts of EG, and 205.7 of PE Part, soybean oil fatty acid 625.3 parts, glycolide 22.7 parts, xylene 50.0 parts were charged, the temperature of the reactor was raised to 160 ° C. and held for 1 hour. Subsequently, the content temperature of the reactor was raised from 160 ° C. to 240 ° C. over 4 hours, and polycondensation proceeded at 240 ° C. while removing the produced condensed water. After confirming that the resin acid value is about 3.0 mgKOH / g or less, heating is stopped, cooling is started, and xylene is added to dilute the polyester resin (A12 ′) having a solid content of 70%. A resin solution was obtained.

  Table 1-2 shows the resin acid values and weight average molecular weights of the polyester resins (A1 ′) to (A18 ′) obtained in each of the above production examples together with the blending amounts of the respective production examples.

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 flask equipped with a stirrer and the liquidus temperature was maintained at 140 ° C. 2, a mixture of each unsaturated monomer shown in FIG. 2 and 1 part of a peroxide-based polymerization initiator “Perbutyl I” (trade name) manufactured by NOF Corporation is dropped into the flask in 3 hours. After completion of the dropping, the temperature was maintained for 30 minutes. Next, a mixture of 10 parts of xylene and 1 part of “Perbutyl I” (trade name) was added dropwise over 20 minutes, and stirring was continued for 2 hours at the same temperature, and then cooling of the liquid phase was started. Furthermore, xylene was added to the flask to prepare a resin solution produced so as to have a solid concentration of 50% by mass to obtain a resin solution of the silyl ester group-containing resin (B1-1).

(Production Examples 19 and 20) Production of silyl ester group-containing resins (B1-2) and (B1-3) A silyl ester was produced in the same manner as in Production Example 18 except that the unsaturated monomers shown in Table 2 were blended. Resin solutions (solid content concentration 50% by mass) of the group-containing resins (B1-2) and (B1-3) were obtained.

Production of Resin (B2) Having Metal Carboxylate Structure (Production Example 21) Production of Resin (B2-1) Having Metal Carboxylate Structure Reaction vessel equipped with thermometer, thermostat, stirrer, reflux condenser and dropping pump Into this, 241.7 parts of xylene, 197.5 parts of butyl acetate, and 241.7 parts of n-butanol were charged, and the temperature of the contents was raised to 105 ° C. while stirring the contents in the reaction vessel. Thereafter, a mixed solution containing 104.2 parts of methacrylic acid, 304.4 parts of ethyl acrylate, 272.4 parts of methoxyethyl acrylate, and 54.5 parts of 2,2-azobis (2-methylbutyronitrile) Was dripped in a reaction vessel maintained at 105 ° C. and uniformly stirred at a constant rate for 4 hours using a dropping pump. An acrylic resin solution was obtained by maintaining the temperature of the contents in the reaction vessel at 105 ° C. for 1 hour after the completion of the dropwise addition of the mixed 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 stirred at 100 ° C. for 20 hours to have a metal carboxylate structure having a nonvolatile content of about 50%. A resin solution of the resin (B2-1) was obtained. The content of metal atoms contained in this 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 In a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping pump, 563.0 parts of xylene and n-butanol 140.7 parts was added, and the temperature of the mixed solution in the reaction vessel was kept at 110 to 120 ° C. In this solution, 281.5 parts of ethyl acrylate, 117.3 parts of 2-ethylhexyl acrylate, 70.4 parts of acrylic acid, 37.5 of 2,2-azobis (2-methylbutyronitrile) Part of the mixed solution was added dropwise at a constant rate over 3 hours. After completion of the dropwise addition of the mixed solution, an acrylic resin solution was obtained by maintaining the temperature of the mixed solution at 110 ° C. to 120 ° C. for 2 hours.

  Furthermore, 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 ° C. and held for 2 hours. During this time, the generated water was removed (dehydration amount of about 30 parts) to obtain a resin solution of resin (B2-2) having a metal carboxylate structure with a nonvolatile content of about 50%. The metal content contained in this resin (B2-2) was 1.08 mol / Kg.

  In addition, metal content, such as zinc and copper, in the resin was quantified by a fluorescent X-ray method.

Preparation of antifouling paint composition and various tests (Examples 1 to 28) and (Comparative Examples 1 to 8), (Examples 29 to 57) and (Comparative Examples 9 to 16)
Evaluation polyester resins (A1) to (A17) and (A1 ′) to (A18 ′) resin solutions, silyl ester group-containing resins (B1-1) to (B1-3), resins having a metal carboxylate structure (B2 -1) and (B2-2) resin solutions, antifouling agents, pigments and the like are blended in the blending compositions shown in Tables 4-1 to 4-4, and stirred at a speed of about 2000 rpm using a homomixer. Mixed and dispersed. After the dispersion, Disparon A630-20XN (manufactured by Enomoto Kasei Co., Ltd., sagging inhibitor) and a solvent were added, and the mixture was stirred with a disper to prepare coating compositions (E1) to (E73). For the prepared coating composition, the following antifouling performance test (test results are shown in Tables 5-1 to 5-4) and adhesion test (Tables 6-1 to 6-4 are shown). ), And crack resistance test (test results are shown in Tables 7-1 to 7-4).

<Anti-fouling performance test>
On both sides of a sandblasted steel plate (100 mm x 300 mm x 2 mm), an epoxy-based anticorrosive paint is spray-coated so as to have a dry film thickness of 200 μm, and further an epoxy-based binder coat is applied so that the dry film thickness becomes 100 μm. Painted. Each coating composition was applied to both sides of this coating plate by spray coating so that the dry film thickness was 480 μm on one side and dried in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75% for one week. A test piece was prepared. Using this test piece, 60 months of seawater immersion was carried out in Shigeura, Minami-Ise-cho, Mie Prefecture, and the proportion of the area occupied by attached organisms (attachment area) on the test coating was measured over time.
◎: (Accepted) No attached organisms were observed ○: (Accepted) The occupied area of attached organisms was less than 5% △: (Failed) The occupied area of attached organisms was 5% or more and less than 30% ×: (Failure ) The area occupied by attached organisms is 30% or more

<Adhesion test>
A sandblasted steel sheet (120 mm x 120 mm x 1 mm) that is curved so that it can be mounted on a cylindrical drum (diameter 500 mm x height 240 mm), and an epoxy-based anticorrosive paint has a dry film thickness of 200 μm. Further, the epoxy-based binder coat was applied so that the dry film thickness was 100 μm. Each coating composition is applied to one side of the coated steel sheet by spray coating so that the dry film thickness is 480 μm, and is dried in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75% for one week. A test piece was prepared. This test piece was mounted on the above cylindrical drum, and the cylindrical drum was rotated for 24 months at 16 knots at 500 mm below the sea surface in Yura Bay, Hyogo Prefecture. Test specimens were collected over time from the sea, 5 mm × 5 mm goby eyes were made, and adhesion was evaluated by tape peeling. Evaluation was based on ISO 2409: 1992.
A: (Pass) Table1 Classification 0 · 1
○: (Pass) Table1 Classification 2
Δ: (Fail) Table 1 Classification 3
X: (failed) Table1 Classification 4.5

<Crack resistance test>
The coating film was visually observed with a test piece subjected to the adhesion test, and the presence or absence of cracks was examined.
◎: (Accepted) No cracks were observed ○: (Acceptable) Minute cracks were slightly observed on the surface of the coating film △: (Failures) Although the coating did not reach the ground, fine and clear cracks were observed Many observed on the surface ×: (Fail) Cracks leading to the ground were observed

Claims (7)

An antifouling paint composition comprising 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),
The said polyester resin (A) has the structural unit represented by following formula (1) in this resin frame | skeleton, and the total mass of the structural unit represented by following formula (1) is the mass of the said polyester resin (A). Is a polyester resin within a range of 2 to 50% by mass based on
The mass ratio of the polyester resin (A) to the total of the silyl ester group-containing resin (B1) and the resin (B2) having the metal carboxylate structure is in the range of 3/97 to 80/20. The antifouling paint composition characterized by the above.

(In the formula, R ₀ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 100.) The silyl ester group-containing resin (B1) is one or more monomers (b1) represented by the following formula (2), and a monomer (b2) other than the monomer (b1) The antifouling paint composition according to claim 1, wherein the antifouling paint composition is a copolymer of one or more of the following.

[Wherein R ₄ represents a hydrogen atom or a methyl group, R ₁ , R ₂ and R ₃ each independently represents a hydrocarbon group, and R ₅ represents a hydrogen atom or R ₆ —O—CO— (where R ₆ represents an organic group or a silyl group represented by —SiR ₇ R ₈ R ₉ , and R ₇ , R ₈ and R ₉ each independently represents a hydrocarbon group. ] The resin (B2) having the metal carboxylate structure has a characteristic group having a metal carboxylate structure represented by the following formula (3), and is included in the resin (B2) having the metal carboxylate structure The content of the metal atom is within the range of 0.04 to 3.50 mol / Kg based on the solid content mass of the resin (B2). Stain paint composition.

(In the formula, M represents a divalent metal atom, and X represents at least one group selected from the group consisting of a hydroxyl group, an organic acid residue, and an alcohol residue.)   The polyester resin (A) is a raw material mixture containing at least one component selected from the group consisting of lactic acid, lactic acid lactide and polylactic acid, and at least one selected from the group consisting of glycolic acid, glycolide and polyglycolic acid A polyester resin produced using at least one raw material mixture of the raw material mixture containing the above components, and the acid value of the polyester resin (A) is in the range of 0.1 to 120 KOHmg / g. The antifouling paint composition according to any one of claims 1 to 3.   The antifouling paint composition according to any one of claims 1 to 4, wherein the polyester resin (A) has a weight average molecular weight in the range of 190 to 15000.   The antifouling paint composition according to any one of claims 1 to 5, wherein the polyester resin (A) does not have a metal carboxylate structure.   The coated article which has a coating film of the antifouling paint composition as described in any one of Claims 1-6.