WO2016151957A1 - Antifouling coating composition and article coated therewith - Google Patents

Abstract

The purpose of the present invention is to provide: an antifouling coating composition capable of forming an antifouling coating film which can retain excellent antifouling properties over a long period and is less apt to suffer coating defects such as coating peeling, blisters, or cracks; and an article obtained by coating a surface of a base, such as a fishing net, ship, marine or bayside structure, etc., with the antifouling coating composition. The present invention is: an antifouling coating composition which comprises a specific polyester resin, a resin having a metal carboxylate structure, and an antifouling agent; and an article which comprises a base having a surface coated with the composition.

Description

Antifouling paint composition and article coated thereby

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

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. An antifouling paint composition containing such a hydrolyzable resin (hereinafter sometimes referred to as “hydrolyzable antifouling paint composition”) is used on the surface of a structure in contact with seawater such as a ship. When the formed coating film comes into contact with seawater, the resin gradually hydrolyzes to dissolve the coating film in the seawater, and the coating surface is continuously renewed to maintain its antifouling performance. Is possible. Although many hydrolyzable antifouling paint compositions containing a resin having a metal carboxylate structure as a resin having hydrolyzability in seawater have been proposed so far, a resin having such a metal carboxylate structure, Since the hydrolysis rate varies depending on the type of metal and the resin structure, it may be difficult to design an antifouling coating composition for maintaining antifouling performance for a long period of time.

Therefore, a method for controlling the dissolution rate of a coating film by using a hydrolyzable antifouling paint composition in which a resin having a metal carboxylate structure and rosin or a rosin derivative are used in combination has been studied (Patent Documents 1 to 3). As described above, by using a resin having a metal carboxylate structure in combination with rosin or a rosin derivative, the dissolution rate of the coating film can be controlled to some extent, but if 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, if the amount of rosin or rosin derivative used is large, the coating film dissolution rate in seawater becomes too large, and the antifouling performance is improved, but the physical properties and adhesion of the coating film are reduced, It was difficult to maintain antifouling performance for a long period of time, and coating film defects such as coating film peeling, blistering, and cracking tended to occur.

JP 2011-32489 A International Publication No. 2011/046087 JP-A-9-286933

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 cracking And an article in which the surface of a base material such as a fishing net, ship, ocean or bay structure is coated with the antifouling coating composition.

The present inventors have intensively studied to achieve the above object, and a coating film obtained from an antifouling coating composition containing a polyester resin and a resin having a metal carboxylate structure is a coating film into the ocean. It is possible to control the dissolution rate, maintain excellent antifouling properties over a long period of time, and further improve the physical properties of the coating film. It has been found that when coating on the bottom of the ship, coating film defects such as coating film peeling, blistering and cracking are less likely to occur during navigation or anchorage. The present invention has been completed based on such findings.

The present invention provides an antifouling paint composition described in the following items, and an article having a substrate surface coated with the antifouling paint composition.
(Item 1) An antifouling paint composition comprising a polyester resin (A), a resin (B) having a metal carboxylate structure, and an antifouling agent (C), wherein the resin (B) having the metal carboxylate structure is A divalent metal atom is contained at a concentration in the range of 0.04 to 3.50 mol / Kg based on the solid content mass of the resin (B), and the polyester resin (A) and the metal carboxylate structure The resin (B) having a mass ratio of 3/97 to 80/20, and the antifouling agent (C) content is the polyester resin (A) and the metal carboxylate structure. The antifouling coating composition, wherein the antifouling coating composition is in the range of 50 to 500% by mass based on the total mass of the resin (B).
(Item 2) The antifouling coating composition according to Item 1, wherein the polyester resin (A) has an acid value in the range of 0 to 120 KOHmg / g.
(Item 3) The antifouling coating composition according to Item 1 or 2, wherein the polyester resin (A) has a weight average molecular weight in the range of 190 to 15000.
(Item 4) Any one of Items 1 to 3, wherein a mass ratio of the polyester resin (A) to the resin (B) having the metal carboxylate structure is within a range of 7/93 to 60/40. The antifouling paint composition described in 1.
(Item 5) The antifouling paint composition according to any one of Items 1 to 4, wherein the polyester resin (A) does not have a metal carboxylate structure.
(Item 6) The resin according to any one of Items 1 to 5, wherein the resin (B) having a metal carboxylate structure contains a characteristic group having a metal carboxylate structure represented by the following general formula (1). Antifouling 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.)
(Item 7) The divalent metal atom contained in the resin (B) having the metal carboxylate structure is at least one metal atom selected from the group consisting of zinc, copper, magnesium, calcium, iron, and tellurium. Item 7. The antifouling paint composition according to any one of Items 1 to 6.
(Item 8) An article, wherein the surface of the substrate is coated with the antifouling coating composition according to any one of Items 1 to 7.

The antifouling paint composition of the present invention is capable of maintaining an excellent antifouling property over a long period of time, and has a coating film in which coating film defects such as coating film peeling, blistering and cracking are unlikely to occur. Can be formed.

The antifouling paint composition of the present invention is an antifouling paint composition comprising a polyester resin (A), a resin (B) having a metal carboxylate structure and an antifouling agent (C), wherein the metal carboxylate structure is The resin (B) having a divalent metal atom at a concentration in the range of 0.04 to 3.50 mol / Kg based on the solid content mass of the resin (B), the polyester resin (A) And the resin having the metal carboxylate structure (B) in a mass ratio of 3/97 to 80/20, and the content of the antifouling agent (C) is the polyester resin (A) It is characterized by being in the range of 50 to 500% by mass based on the total mass with the resin (B) having the metal carboxylate structure. Hereinafter, the antifouling coating composition of the present invention will be described in detail.

[Polyester resin (A)]
The polyester resin (A) used in the antifouling paint composition of the present invention uses an acid component (a1) and an alcohol component (a2) as main components, and by esterification and / or transesterification of these components. Can be manufactured.

Acid component (a1)
In this invention, the acid component (a1) can use the acid component normally used for manufacture of a polyester resin. Examples of such acid components include alicyclic polybasic acids, aliphatic polybasic acids, aromatic polybasic acids, aromatic monocarboxylic acids, aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and 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 acid anhydrides of the compounds, 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, 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, 1,2 Alicyclic polycarboxylic acids such as 1,4-cyclohexanetricarboxylic acid and 1,3,5-cyclohexanetricarboxylic acid; anhydrides of these alicyclic polycarboxylic acids; lower alkyl esters of these alicyclic polycarboxylic acids These 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 brassic acid. Aliphatic polycarboxylic acids such as octadecanedioic acid and citric acid; anhydrides of these aliphatic polyvalent carboxylic acids; halides of these aliphatic polyvalent carboxylic acids, and the like. The above 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 polybasic 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 3 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 alkyls of melophanic acid, and melophanic acid halides; and 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, lactic 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. Acid, stearic acid, oleic acid, elaidic acid, brassic acid, linoleic acid, linolenic acid, rosin acid, coconut oil fatty acid, cottonseed oil fatty acid, hemp oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, flaxseed Saturated or unsaturated aliphatic monocarboxylic acids such as oil fatty acids, tung oil fatty acids, rapeseed oil fatty acids, castor oil fatty acids, dehydrated castor oil fatty acids, safflower oil fatty acids, and the like are used alone or in combination of two or more. Can be used.

Examples of the alicyclic monocarboxylic acid include cyclohexanecarboxylic acid, cyclopentanecarboxylic acid, cycloheptanecarboxylic acid, 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-laurylcyclohexanecarboxylic acid, and the like. These can be used alone or in combination of two or more.

In the present invention, the acid component (a1) used in the production of the polyester resin (A) may contain an esterified product such as a 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 Based on the total number of moles of the acid 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 a dihydric alcohol such as an alicyclic diol, an aliphatic diol, an aromatic diol and / or a trihydric or higher polyhydric alcohol 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.

If necessary, 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, and the like; ethylene oxide, propylene oxide, butylene oxide, glycidyl esters of synthetic hyperbranched saturated fatty acids (trade name “Cardura E10”, manufactured by HEXION Specialty Chemicals) and the like Alcohol compound obtained by reacting with a compound having a protonic acid; containing metal having a metal carboxylate structure such as zinc lactate Well as alcohol compounds can be used as a secondary raw material for producing the polyester resin (A).

In the present invention, the production method of the polyester resin (A) is not particularly limited, and a normal method can be adopted. For example, the polyester resin (A) comprises one or more acid components (a1) and one or more alcohol components (a2) at 150 ° C. to 250 ° C. in a nitrogen stream. It can be produced by reacting at a temperature for 2 to 10 hours to carry out an esterification reaction and / or a transesterification reaction. In the esterification reaction and / or transesterification reaction, the acid component (a1) and alcohol component (a2) may be added at once, or may be added in a plurality of times. The above reaction may be performed in the presence of a known organic solvent.

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

Further, the esterification reaction and / or transesterification 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) is produced by an esterification reaction and / or a transesterification reaction of these components, with the acid component (a1) and the alcohol component (a2) as main components. Accordingly, a known organic and / or inorganic compound other than the acid component (a1) and the alcohol component (a2) may be included as a component, and amidation reaction, urethanization reaction, imidation reaction, carbonate It may be produced with a known chemical reaction such as a hydrogenation reaction or a urea reaction. For example, in the polyester resin (A), during or after the esterification reaction and / or transesterification reaction, the reaction intermediate or reaction product is converted into an organic acid zinc, organic acid copper, zinc chloride, copper chloride, hydroxylation. Metal compounds such as zinc, copper hydroxide, zinc oxide, copper oxide, fatty acids, fats and oils, mono- or polyisocyanate compounds, mono- or polyamine compounds having nitrogen bonded to hydrogen atoms, epoxy compounds, acrylic resins, vinyl ester resins, etc. It may be a modified polyester resin obtained by reacting.

In addition, although the polyester resin (A) in this invention may have a metal carboxylate structure, the solid content mass of the said polyester resin (A) of the metal atom contained in the said metal carboxylate structure in that case Is preferably lower than the concentration of metal atoms contained in the resin (B) having a metal carboxylate structure, which will be described later, and less than 0.04 mol / Kg. Furthermore, the polyester resin (A ) Is more preferably substantially free of the metal carboxylate structure described above. 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 such as a pigment component or an antifouling agent component, the metal carboxylate structure is formed during the production or storage of the antifouling paint composition. The polyester resin (A), which does not substantially have, may react with the component containing the metal compound to form a metal carboxylate structure over time. The concentration 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. / Kg, preferably less than 0.04 mol / Kg.

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

The acid value of the polyester resin (A) is preferably in the range of 0 to 120 mgKOH / g, from the viewpoint of maintaining the antifouling property of the resulting coating film over a long period, and is preferably 0 to 95 mgKOH / g. Is more preferable, and a range of 0 to 45 mgKOH / g is particularly preferable.

Furthermore, the weight average molecular weight of the polyester resin (A) is preferably in the range of 190 to 15000, from the viewpoint of antifouling properties of the resulting coating film and maintaining antifouling properties for a long period of time. Is more preferable, and a range of 600 to 8000 is particularly preferable.

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

[Resin having metal carboxylate structure (B)]
In addition to the polyester resin (A), the antifouling coating composition of the present invention is a resin (B) having a metal carboxylate structure (in the present specification, this “resin (B) having a metal carboxylate structure”). May be simply referred to as “resin (B)”. As the resin (B), a known resin can be used without being limited by the type and composition of the resin as long as it has a metal carboxylate structure.

Examples of the resin (B) include those containing a characteristic group having a metal carboxylate structure represented by the following general formula (1).

(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 general formula (1) include zinc, copper, magnesium, calcium, iron and tellurium, and zinc or copper is preferable.

The resin (B) containing the characteristic group (b1) having a metal carboxylate structure in which X in the general formula (1) is a hydroxyl group includes, for example, a known resin having a carboxyl group and 1 mol of the carboxyl group in the resin. 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 moles with respect to 1 mole of the carboxyl group. When the amount of water is less than 0.1 mol, the structural viscosity increases, and it may be difficult to handle the resin (B) having a metal carboxylate structure. On the other hand, when the amount of water exceeds 10.0 mol, an excessive water separation operation may be required.

As a specific method for producing the resin (B) containing the characteristic group (b1), for example, a resin having a carboxyl group, water, and a divalent metal compound are placed in a reaction vessel, and 50 ° C. to Examples include a method of reacting at a temperature of 150 ° C. for 1 to 20 hours. 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 in the production of the resin (B) containing the characteristic group (b1), 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.

In addition, as the resin having a carboxyl group used for the production of the resin (B) containing the characteristic group (b1), for example, a resin such as a vinyl polymer, polyester, polyurethane, or natural resin can be used. However, in terms of 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. A vinyl polymer obtained by copolymerizing with another unsaturated monomer can be preferably used.

Moreover, as resin (B) containing the characteristic group (b2) which has a metal carboxylate structure whose X in the said General formula (1) is an organic acid residue, for example, the unsaturated monomer containing a characteristic group (b2) A polymer of the body (b2m) or a copolymer of two or more, one or more of the unsaturated monomer (b2m) containing the characteristic group (b2) and the unsaturated monomer (b2m) Examples thereof include a copolymer with one or more of unsaturated monomers (m1), or an arbitrary resin containing these polymers or copolymers as a structural unit.

Here, as said unsaturated monomer (b2m), what is represented by the following general formula (2) or (3) is mentioned, for example.

(In the general formula (2) or (3), R ¹ and R ² represent a hydrogen atom or a methyl group, A represents an organic acid residue, and M represents a divalent metal atom.)

Among the unsaturated monomers (b2m), as a method for producing the unsaturated monomer (b2m-1) represented by the general formula (2), for example, polymerizable monomers such as (meth) acrylic acid can be used. A method of reacting a saturated organic acid, a metal compound such as a divalent metal oxide, hydroxide, or salt with a monobasic organic acid capable of forming an organic acid residue; 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 (b2m), the method for producing the unsaturated monomer (b2m-2) represented by the above general formula (3) includes, for example, a polymerizable monomer such as (meth) acrylic acid. Examples thereof include a method in which a saturated organic acid is reacted 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 general formula (1) 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, 2-ethylhexyl. 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 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, parastolic acid, pima Examples thereof include those derived from organic acids such as phosphoric acid, isopimaric acid, levopimaric acid, dextropimaric acid, sandaracopimaric acid, resin acid, abietane, pimaran, isopimaran, and a compound 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 General formula (2).

Specific examples of the unsaturated monomer (b2m-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 caprate (meth) acrylate, magnesium 2-ethylhexylate (meth) acrylate, zinc 2-ethylhexylate ( (Meth) acrylate, copper 2-ethylhexylate (meth) acrylate, magnesium caprate (meth) acrylate, zinc caprate (meth) acrylate, copper caprate (meth) acrylate, versatic acid magnesium (meth) acrylate, versatic acid zinc ( (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, zinc naphthoate (meth) acrylate, copper naphthoate (meth) acrylate, magnesium naphthoate (meth) acrylate, zinc naphthoate (meth) acrylate, β- Naphthoic acid copper (meth) acrylate, magnesium benzoate (meth) acrylate, zinc benzoate (meth) acrylate, copper benzoate (meth) acrylate, 2,4,5-trichlorophenoxymagnesium acetate (meth) acrylate, 2,4 , 5-trichlorophenoxyacetate zinc (meth) acrylate, 2,4,5-trichlorophenoxyacetate copper (meth) acrylate, 2,4-dichlorophenoxyacetate magnesium (meth) acrylate, 2,4-dichlorophenoxyacetate 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 can be used by appropriately selecting one type or two or more types as necessary.

Examples of the unsaturated monomer (b2m-2) represented by the general formula (3) 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 can be used by appropriately selecting one or two or more kinds as necessary. Among these unsaturated monomers, the antifouling property of the obtained coating film is long. From the viewpoint of maintaining the period, it is preferable to use zinc (meth) acrylate.

The resin (B) containing the characteristic group (b3) having a metal carboxylate structure in which X in the general formula (1) is an alcohol residue is, 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 with one or more of the bodies (m2), or any resin containing these polymers or copolymers as a structural unit.

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.

The amount of the unsaturated monomer (b2m-1) used to obtain the resin (B) containing the characteristic group (b2) is selected from the viewpoint of maintaining the antifouling property of the obtained coating film for a long period of time. It is preferably in the range of 0.5 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 (B).

The amount of the unsaturated monomer (b2m-2) used for obtaining the resin (B) containing the characteristic group (b2) is from the viewpoint of maintaining the antifouling property of the obtained coating film for a long period of time. The content is preferably in the range of 0.5 to 50.0% by mass, more preferably in the range of 1.0 to 30.0% by mass, based on the solid content mass of the resin (B).

Further, the resin (B) includes at least one unsaturated monomer selected from the group consisting of the unsaturated monomers (b2m-1), (b2m-2) and (b3m), and, if necessary. It can also be obtained by copolymerizing one or more of the unsaturated monomers (m3) other than these at an arbitrary ratio.

The unsaturated monomers (m1), (m2) and (m3) may be the same or different. Examples of the unsaturated monomers (m1), (m2) and (m3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- Butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, Tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) Alkyl or cycloalkyl (meth) acrylates such as acrylate and cyclododecyl (meth) acrylate; monomers having an isobornyl group such as isobornyl (meth) acrylate; monomers having an adamantyl group such as adamantyl (meth) acrylate; styrene , Α-methylstyrene, vinyltoluene and other vinyl aromatic compounds; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meta ) Monomers having alkoxysilyl groups such as acryloyloxypropyltriethoxysilane; perfluoroalkyls such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate (Meth) acrylate; monomer having a fluorinated alkyl group such as fluoroolefin; N-substituted maleimides; vinyl compounds such as N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate; (meth) acrylic acid, Carboxyl group-containing monomers such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, crotonic acid, β-carboxyethyl (meth) acrylate; (meth) acrylonitrile, (meth) acrylamide, N, N-dimethyl (Meth) acrylamide, (meth) acryloylmorpholine, N-isopropyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylic Nitrogen-containing monomers such as adducts, N, N-dimethylaminopropyl (meth) acrylamide, adducts of glycidyl (meth) acrylate and amines; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Monoesterified products of (meth) acrylic acid such as acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like, and (meth) acrylic acid Hydroxyl group-containing monomers such as ε-caprolactone modified monoester compounds with dihydric alcohols having 2 to 8 carbon atoms, allyl alcohol, (meth) acrylates having a polyoxyethylene chain having a hydroxyl group at the molecular end; glycidyl (meta ) Acrylate, β-methylglycidyl (meth) acrylate, 3, 4 Epoxy group-containing monomers such as epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether; (Meth) acrylate having an oxyethylene chain; 2- (meth) acrylamide-2-methylpropanesulfonic acid, allylsulfonic acid, styrenesulfonic acid, sulfoethyl (meth) acrylate and sulfonic acid groups such as sodium salt or ammonium salt thereof Containing monomer; Monomer having a phosphate group such as 2- (meth) acryloyloxyethyl acid phosphate; acrolein, diacetone (meth) acrylamide, acetoacetoxyethyl (meth) A carbonyl group-containing monomer such as acrylate, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone); allyl (meth) acrylate, ethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, glycerin Di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, neopentyl glycol diacrylate, 1, 6-hexanediol di (meth) acrylate, glycerol allyloxydi (meth) acrylate, 1,1,1-tris (hydroxymethyl) ethanedi (meth) acrylate, 1,1,1-tris (hydroxymethyl) ethanetri (meta ) Acrylate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, diallyl isophthalate, pentaerythritol diallyl ether, divinylbenzene, Chirenbisu (meth) acrylamide, ethylenebis (meth) polymerizable unsaturated monomer polymerizable unsaturated groups having 2 or more in one molecule of acrylamide; and the like and combinations of two or more thereof may be mentioned.

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.

The resin (B) 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 relative to 1 mol of the carboxyl group in the resin. It may be produced by reacting an oxide or hydroxide of the above with an organic acid, an alcohol compound, water or the like, if necessary, at a temperature of 50 to 200 ° C. for 1 to 20 hours. X in the characteristic group having a metal carboxylate structure represented by the general formula (1) contained in the resin (B) produced by this reaction is selected from the group consisting of a hydroxyl group, an organic acid residue, and an alcohol residue. It suffices if it is at least one selected group, and the constituent ratio is not particularly limited.
This reaction may be performed in the presence of a suitable organic solvent. 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.

The divalent metal compound used for the production of the resin (B) can be any known one without particular limitation. However, zinc, copper, magnesium, 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 calcium, iron and tellurium is preferred, and an oxide, salt or hydroxide of zinc or copper is more preferred.

As the resin having a carboxyl group, for example, resins such as vinyl polymer, polyester, polyurethane, and natural resin can be used. However, (meth) acrylic acid and maleic acid are preferable in that the degree of freedom of composition change is large. A vinyl polymer obtained by copolymerizing a carboxyl group-containing unsaturated monomer such as fumaric acid or itaconic acid with another unsaturated monomer such as (meth) acrylic acid alkyl ester or styrene, Can be used.

The resin (B) containing the characteristic group (b2) 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 (1) contained in the resin (B) having a metal carboxylate structure is a hydroxyl group, an organic acid residue, and an alcohol residue. The concentration of the metal atom contained in the metal carboxylate structure may be 0.04 to 3 based on the solid content mass of the resin (B). 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 concentration of the metal atom is more than 3.50 mol / Kg, the period during which the antifouling property of the obtained coating film can be maintained may be shortened. When the concentration 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 (B) having a metal carboxylate structure include, for example, 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. And a polyaddition reaction or a condensation reaction.

[Anti-fouling agent (C)]
The antifouling paint composition of the present invention further contains an antifouling agent (C) in addition to the polyester resin (A) and the resin (B) having the metal carboxylate structure. 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, and in addition, manneb, manceb, propineb, or the like can also be used. Further, examples of the organic copper-based 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, for example, N-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino-1,3-thiazolidine-2,4-dione, dithiocyano compounds, and triazine compounds. 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, 2,5-dithiocyanothiophene, and the like.

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.

The antifouling agent (C) can be used alone or in combination of two or more of the compounds exemplified above. 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 article with which the surface of the substrate is coated]
As described above, the antifouling coating composition of the present invention is an antifouling coating composition comprising a polyester resin (A), a resin (B) having a metal carboxylate structure, and an antifouling agent (C), wherein the metal Resin (B) having a carboxylate structure contains a divalent metal atom at a concentration in the range of 0.04 to 3.50 mol / Kg based on the solid content mass of the resin (B), The mass ratio of the resin (A) to the resin (B) having the metal carboxylate structure is in the range of 3/97 to 80/20, and the content of the antifouling agent (C) is the polyester resin. It is characterized by being in the range of 50 to 500% by mass based on the total mass of (A) and the resin (B) having the metal carboxylate structure.

The mass ratio of the polyester resin (A) and the resin (B) having a metal carboxylate structure is in the range of 3/97 to 80/20, preferably in the range of 7/93 to 60/40. More preferably, it is in the range of 10/90 to 50/50. When the mass ratio of the polyester resin (A) and the resin (B) having a metal carboxylate structure is in the range of 3/97 to 80/20, the antifouling performance of the resulting antifouling coating film is excellent. In the antifouling coating film, coating film defects such as coating film peeling, blistering, and cracking are less likely to occur. When the mass ratio of the polyester resin (A) and the resin (B) having the metal carboxylate structure is smaller than 3/97 or larger than 80/20, the antifouling performance of the obtained coating film is increased. It may be difficult to maintain the period.

In the antifouling coating composition of the present invention, the content of the antifouling agent (C) is 50 to 500 on the basis of the total mass of the polyester resin (A) and the resin (B) having the metal carboxylate structure. It is in the range of mass%, but is 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 for a long period of time. When there is more content 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.

The antifouling coating composition of the present invention comprises, in addition to the above-described polyester resin (A), resin (B) having a metal carboxylate structure, and antifouling agent (C), pigments, dyes, dehydrating agents, plasticizers, soot General coating compositions such as modifiers (sagging agents), antifoaming agents, antioxidants, resins other than the polyester resin (A) or the resin having a metal carboxylate structure (B), organic acids, solvents, etc. Various components used in the product 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 in the range of 0.05 to 1000% by mass based on the total mass of the polyester resin (A) and the resin having a metal carboxylate structure (B). Preferably, it is in the range of 1 to 500% by mass.

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)), and others. Examples include esters (for example, methyl orthoformate, methyl orthoacetate, orthoborate, etc.), silicates, isocyanates, and the like. Among these, anhydrous gypsum and hemihydrate gypsum (calcined gypsum) which are inorganic dehydrating agents are preferable. These dehydrating agents may be used alone or in combination of two or more. The content of the dehydrating agent in the antifouling coating composition can be adjusted as appropriate, but it is 0 to 100 based on the total mass of the polyester resin (A) and the resin (B) having a metal carboxylate structure. It is preferably in the range of mass%, more preferably in the range of 0.5 to 25 mass%.

The above plasticizer is a component that contributes to improving the 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), polyvinylethyl. Examples include ether. These plasticizers may be used alone or in combination of two or more. In addition, when mix | blending a plasticizer with the antifouling-coating composition of this invention, content of the plasticizer in the said antifouling-coating composition is polyester resin (A) and resin (B) which has a metal carboxylate structure. Is preferably in the range of 0.5 to 10% by mass, 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. When blending the antifouling coating composition of the present invention with a discoloring agent, the content of the discoloring agent in the antifouling coating composition can be adjusted as appropriate. For example, polyester resin (A) and metal It is in the range of 0.25 to 50% by mass based on the total mass with the resin (B) having a carboxylate structure.

The antifouling coating composition of the present invention contains one or more other resins as required in addition to the polyester resin (A) and the resin (B) having a metal carboxylate structure as described above. You may contain. Examples of such resins include silyl ester group-containing resins, acrylic resins, acrylic silicone resins, epoxy resins, fluororesins, polybutene resins, silicone rubbers, urethane resins, which are widely used as base resins for antifouling paints. , Polyamide resin, vinyl chloride copolymer resin, chlorinated rubber, chlorinated olefin resin, styrene / butadiene copolymer resin, ketone resin, ethylene-vinyl acetate copolymer resin, vinyl chloride resin, alkyd resin, coumarone resin, terpene phenol resin And petroleum resin.

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 50 mass% or less is preferable on the basis of the total mass with resin (B) which has a metal carboxylate structure, and 30 mass% or less is still more preferable.

The antifouling paint composition of the present invention comprises an aliphatic solvent, an aromatic solvent (eg, xylene, toluene, etc.), a ketone solvent (eg, methyl isobutyl ketone, cyclohexanone, etc.), an ester solvent, an ether solvent (eg, propylene glycol monomethyl). Organic solvents generally used as solvents for antifouling paints such as ether, propylene glycol monomethyl ether acetate, etc., alcohol solvents (eg, isopropyl alcohol, etc.) can be blended. The blending amount of the organic solvent can be adjusted as appropriate. For example, the blending amount is such that the total solid content of the antifouling coating composition is in the range of 20 to 90% by mass. You may add further according to property etc.

The antifouling paint composition of the present invention can be prepared by the same method as known antifouling paint compositions. For example, the polyester resin (A), the resin (B) having a metal carboxylate structure, the antifouling agent (C), and, if necessary, the organic solvent and additives are added to the stirring tank at once or sequentially. It can be manufactured by adding, stirring and mixing.

The article of the present invention is an article in which the surface of the substrate is coated with the antifouling paint composition of the present invention. The article is obtained by a method comprising 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 antifouling coating composition applied or impregnated. ,Obtainable.

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 / time, preferably about 75 to 150 μm / time, and may be applied twice or more as necessary.

In obtaining the article, after applying a primer, anticorrosive paint, and, if necessary, a binder paint on the surface of the substrate, means such as brush coating, spray coating, roller coating, dipping, etc. are applied to the coated surface. The antifouling coating composition of the present invention may be applied by 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.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to only the examples. 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, 527.2 parts of PA, 267.2 parts of NPG, 269.7 parts of DEG 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 was 1.0 mgKOH / g or less, heating was stopped and cooling was started, and xylene was 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

(Production Examples 2 to 12, 16, and 17) Production of polyester resins (A2) to (A12), (A16), and (A17) Except that the acid component and alcohol component in Production Example 1 were formulated as shown in Table 1. In the same manner as in Production Example 1, polyester resins (A2) to (A12), (A16) and (A17) having a solid content of 70% were obtained. In Production Example 17, it was difficult to set the acid value of the produced polyester resin to 1.0 mgKOH / g or less, so the reaction was terminated at a slightly higher acid value.

Production Example 13 Production of Polyester Resin (A13) A 2 L reactor equipped with a thermometer, a stirrer, and a rectifying tower was charged with 377.8 parts iPA, 364.2 parts BEPG, and 227.6 parts TEG. 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 1.0 mgKOH / g or less, the content temperature was cooled to 160 ° C. Further, 112.3 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 (A13) having a solid content of 70%.

(Production Example 14) Production of polyester resin (A14) A polyester resin (A14) having a solid content of 70% was produced in the same manner as in Production Example 13 except that the acid component and alcohol component in Production Example 13 were formulated as shown in Table 1. ) Resin solution was obtained.

(Production Example 15) Production of polyester resin (A15) In a 2 L reactor equipped with a thermometer, a stirrer and a water separator, 237.5 parts of PA, 29.3 parts of EG, 198.2 parts of PE, 602.6 parts of soybean oil fatty acid and 50.0 parts of xylene were charged, and 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 while removing the produced condensed water while maintaining the temperature at 240 ° C. After confirming that the acid value of the produced polyester resin was about 3.0 mgKOH / g, heating was stopped, cooling was started, and xylene was added to dilute to obtain a polyester resin having a solid content of 70% ( A resin solution of A15) was obtained.

The acid values and weight average molecular weights of the polyester resins (A1) to (A17) obtained in each of the above production examples are shown in Table 1 together with the blending amounts of the respective production examples.

Production of resin (B) having a metal carboxylate structure (Production Example 18) Production of resin (B1) having a metal carboxylate structure In a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping pump, 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. 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 52%. A resin solution of the resin (B1) was obtained.

(Production Examples 19 to 20) Production of Resins (B2) and (B3) having a Metal Carboxylate Structure Same as Production Example 18 except that the unsaturated monomers in Production Example 18 were formulated as shown in Table 2. By carrying out the synthesis under the reaction conditions, resin solutions (B2) and (B3) having a metal carboxylate structure with a solid content of 50% were obtained.

Production Example 21 Production of Resin (B4) 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 140 of n-butanol .7 parts charged, while maintaining the temperature of the contents (solution) in the reaction vessel between 110 ° C. and 120 ° C., 281.5 parts of ethyl acrylate and 117. 2-ethylhexyl acrylate were added to this solution. A mixed solution containing 3 parts, 70.4 parts of acrylic acid and 37.5 parts of 2,2-azobis (2-methylbutyronitrile) was added dropwise at a constant rate over 3 hours. An acrylic resin solution was obtained by maintaining the temperature of the contents in the reaction vessel between 110 ° C. and 120 ° C. for 2 hours after the dropwise addition of the mixed solution.
Furthermore, after adding 236.4 parts of naphthenic acid and 82.8 parts of copper hydroxide to the obtained resin solution, the temperature was raised to 120 ° C., and this state was removed while removing generated water (dehydration amount). About 30 parts) By holding for 2 hours, a resin solution of resin (B4) having a metal carboxylate structure with a nonvolatile content of about 50% was obtained.

(Production Examples 22 to 23) Production of Resins (B5) and (B6) having a Metal Carboxylate Structure Same as Production Example 21 except that the unsaturated monomers in Production Example 21 were formulated as shown in Table 2. By carrying out the synthesis under reaction conditions, resin solutions of resins (B5) and (B6) having a metal carboxylate structure were obtained.

Production Example 24 Production of Resin (B7) Having Metal Carboxylate Structure In a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping pump, 255.2 parts of xylene and 208. of butyl acetate. 4 parts and 255.2 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, 115.0 parts of zinc diacrylate salt (manufactured by NOF Corporation), 321.3 parts of ethyl acrylate, 287.5 parts of methoxyethyl acrylate, 2,2-azobis (2-methylbutyronitrile) Was added dropwise to the reaction vessel at a constant rate over 4 hours. After completion of the dropwise addition of the mixed solution, the temperature of the content in the reaction vessel is continuously maintained at 105 ° C. for 3 hours to obtain a resin solution of resin (B7) having a metal carboxylate structure with a nonvolatile content of about 52%. It was.

Production Example 25 Production of Resin (B8) Having Metal Carboxylate Structure In a reaction vessel equipped with a stirrer, a water separator and a thermometer, 177.7 parts of ethylene glycol and 441.4 parts of hexahydrophthalic anhydride Then, 121.1 parts of trimellitic anhydride was charged, and the contents in the reaction vessel were gradually heated to 180 ° C. Next, the content in the reaction vessel was heated from 180 ° C. to 200 ° C. over 2 hours while removing the generated condensed water. Then, reaction was performed at 200 degreeC for 4 hours, and the polyester whose acid value of resin is 150 mgKOH / g was obtained. The resulting polyester was cooled, and 233.6 parts of xylene, 233.6 parts of butyl acetate, 233.6 parts of n-butanol, 34.1 parts of deionized water, and 76.6 parts of zinc oxide were added. Thereafter, a reaction was carried out at 100 ° C. for 8 hours to obtain a resin (B8) having a metal carboxylate structure. The metal content contained in this resin (B8) was 1.26 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 27) and (Comparative Examples 1 to 5)
Polyester resins (A1) to (A17) evaluated , resin solutions (B1) to (B8) having a metal carboxylate structure, antifouling agents, pigments, and the like in the composition shown in Tables 3 and 4 The mixture was mixed and dispersed using a homomixer at a stirring speed of about 2,000 rpm. After dispersion, Disparon A630-20XN (manufactured by Enomoto Kasei Co., Ltd., sagging inhibitor) and a solvent were added and stirred with a disper to prepare coating compositions (E1) to (E32). The prepared coating composition was subjected to the following antifouling performance test, adhesion test, and crack resistance test. The results of each of these tests are also shown in Tables 3 and 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, 48 months of seawater immersion was carried out in Owase Bay, Mie Prefecture, and the ratio 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 was applied to one side of the coated steel plate by spray coating so that the dry film thickness was 480 μm on one side, and dried for one week in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75%. 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, and a Gobang eye test was conducted at intervals of 5 mm. 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.
A: (Pass) No crack was observed. ○: (Pass) A fine crack was observed in a part of the surface of the coating film. Δ: (Fail) A fine or clear crack was in a wide range of the coating surface. X: (Fail) Cracks leading to the ground were observed

Claims (8)

1. An antifouling paint composition comprising a polyester resin (A), a resin having a metal carboxylate structure (B) and an antifouling agent (C),
   The resin (B) having the metal carboxylate structure contains a divalent metal atom at a concentration in the range of 0.04 to 3.50 mol / Kg based on the solid content mass of the resin (B),
   The mass ratio of the polyester resin (A) and the resin (B) having a metal carboxylate structure is in the range of 3/97 to 80/20, and the content of the antifouling agent (C) is The antifouling coating composition, wherein the antifouling coating composition is in the range of 50 to 500% by mass based on the total mass of the polyester resin (A) and the resin (B) having the metal carboxylate structure.
2. The antifouling paint composition according to claim 1, wherein the acid value of the polyester resin (A) is in the range of 0 to 120 KOHmg / g.
3. The antifouling paint composition according to claim 1 or 2, wherein the polyester resin (A) has a weight average molecular weight in the range of 190 to 15000.
4. The prevention according to any one of claims 1 to 3, wherein a mass ratio of the polyester resin (A) to the resin (B) having the metal carboxylate structure is within a range of 7/93 to 60/40. Stain paint composition.
5. The antifouling paint composition according to any one of claims 1 to 4, wherein the polyester resin (A) does not have a metal carboxylate structure.
6. The antifouling agent according to any one of claims 1 to 5, wherein the resin (B) having a metal carboxylate structure contains a characteristic group having a metal carboxylate structure represented by the following general formula (1). 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.)
7. The divalent metal atom contained in the resin (B) having the metal carboxylate structure is at least one metal atom selected from the group consisting of zinc, copper, magnesium, calcium, iron and tellurium. The antifouling paint composition according to any one of 1 to 6.
8. An article in which the surface of a substrate is coated with the antifouling paint composition according to any one of claims 1 to 7.