TWI468480B - Manufacturing method of resin dispersions for anti-fouling paint - Google Patents

Description

Method for producing resin dispersion for antifouling coating

The present invention relates to a method for producing a resin dispersion for an antifouling coating using a resin of an aqueous dispersion type metal. More specifically, the present invention relates to a method for producing a resin dispersion for an antifouling coating which can form a coating film for preventing sea creatures and seaweed from adhering to underwater structures, fishing nets, and ship bottoms.

The coating film formed of the antifouling paint exhibits an antifouling effect by being eluted into the sea by the antifouling agent component contained therein. When the coating film formed by the disintegrating antifouling paint using a rosin-based compound is immersed in the sea for a long period of time, the elution component gradually decreases, and the insoluble component gradually increases. Therefore, the coating film surface is uneven, and the sea is in the sea. The adhesion prevention effect of living organisms and the like is remarkably lowered.

On the other hand, the coating film formed by the self-polishing antifouling paint is characterized in that the surface of the coating film is gradually surface-renewed (self-polishing), and the antifouling component is always exposed on the surface of the coating film to exert a long-term antifouling effect. . However, these coating materials contain a large amount of various organic solvents such as xylene or alcohol, and various antifouling coatings for replacing these antifouling coatings have been studied due to the problem of volatile organic compounds (VOC) in recent years.

As a self-polishing antifouling paint, for example, Patent Document 1 discloses an antifouling paint composition containing a resin composition containing a metal atom at a terminal portion of a side chain. The resin of the group. Further, as the metal atom, zinc (Zn), copper (Cu), and tellurium (Te) are described.

Patent Document 2 proposes a water-based antifouling paint composition comprising a resin containing a divalent metal, water, and a basic compound, and further containing an alcohol compound. Cu, Zn, magnesium (Mg), and calcium (Ca) are described as the divalent metal, and ammonia and an amine are described as a basic compound. Further, in Patent Document 2, the divalent metal-containing resin is obtained by polymerizing a monomer mixture containing a divalent metal-containing polymerizable monomer.

Patent Document 3 proposes an aqueous resin dispersion liquid having a unit containing a divalent metal and a unit derived from a reactive emulsifier. In the case of the divalent metal, Cu, Zn, Mg, and Ca are described, and the resin aqueous dispersion is a mixture of a polymerizable monomer containing a divalent metal, a reactive emulsifier, and an organic solvent. The solution is solution-polymerized and subjected to a solvent removal treatment as needed, followed by mixing with water.

Patent Document 4 proposes an aqueous antifouling paint containing a carboxyl group and/or a metal carboxylate group in a resin molecule and having a resin acid value obtained by emulsion polymerization of 10 mg KOH/g to 300 mg KOH/ An aqueous resin emulsion of g, and an aqueous metal complex containing a carboxylic acid and a divalent or higher metal, as needed. As the metal, Cu, Zn, Ca, Mg, Zr, and Fe are described.

Patent Document 5 proposes an aqueous antifouling resin composition comprising an aqueous resin emulsion as an antifouling adhesive, wherein the aqueous resin emulsion is formed by dispersing a resin obtained by dispersing a resin in an emulsifier. a metal carboxylate formed by having a molar ratio of a carboxyl group to a divalent metal in a matrix resin having an acid value of 10 mg KOH/g to 300 mg KOH/g in the molecule and/or between molecules. Structure of the resin. As the divalent metal, Cu, Zn, Ca, and Mg are described.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 62-57464

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-49123

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-23243

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-109729

[Patent Document 5] Japanese Patent Laid-Open No. Hei 11-172159

However, the antifouling paint described in Patent Document 1 is used in a state of being dissolved in a general organic solvent, and does not satisfy the desired water-based environmental hygiene in recent years.

The aqueous antifouling paint of Patent Document 2 contains a large amount of a basic compound which is coordinated to a divalent metal, so that the basic compound remains in the coating film, the water resistance is low, and the adhesion of the coating film is problematic.

Since the aqueous antifouling paint of Patent Document 3 uses a reactive emulsifier as a structural unit of the copolymer, a hydrophilic unit such as an alkylene oxide derived from an emulsifier remains in the coating film, and is coated in a long-term test. There is a problem with water resistance.

In the aqueous antifouling paint of Patent Document 4, when an aqueous metal complex of a carboxylic acid and a metal and a basic compound is prepared in order to supplement the deficiency of the divalent metal-containing monomer component introduced into the resin in the emulsion polymerization, The basic compound remains in the coating film, and the water resistance and long-term antifouling properties of the coating film are low, and the adhesion of the coating film is problematic.

The aqueous antifouling resin composition of Patent Document 5 is prepared by dissolving an emulsifier in a resin dissolved in an organic solvent such as xylene or butyl acetate, and diluting with water to form a forced emulsification. The resin component is easily precipitated and stored. The separation between the aqueous layer and the resin-containing layer is separated, so that the storage stability of the emulsion is problematic.

An object of the present invention is to provide a self-abrasive resin dispersion for an antifouling coating which is excellent in storage stability and water resistance in seawater, and which exhibits an antifouling effect for a long period of time and is excellent in adhesion.

The method for producing a resin dispersion for an antifouling coating of the present invention comprises the steps of producing a divalent metal-containing polymer (A), and dispersing the polymer (A) in a dispersion medium containing water or a water/organic solvent mixture The method for producing a resin dispersion for an antifouling coating is characterized in that the divalent metal-containing polymer (A) is a divalent metal-containing ethylenically unsaturated monomer in an amount of from 1% by weight to 40% by weight. (a1), 0 to 8 wt% of a carboxyl group-containing ethylenically unsaturated monomer (a2), 0 to 40% by weight of a hydroxyl group-containing ethylenically unsaturated monomer (a3), and 99 to 22% by weight of other ethylenicity The unsaturated monomer (a4) is a polymer obtained by solution polymerization in a plurality of stages of two or more stages.

[Effects of the Invention]

According to the present invention, it is possible to provide a resin dispersion for an antifouling coating having self-lubricating property which is excellent in storage stability and water resistance in seawater, and which exhibits an antifouling effect for a long period of time and is excellent in adhesion.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

The method for producing a resin dispersion for an antifouling coating of the present invention comprises the steps of producing a divalent metal-containing polymer (A), and dispersing the polymer (A) in a dispersion medium containing water or a water/organic solvent mixture The method for producing a resin dispersion for an antifouling coating is characterized in that the divalent metal-containing polymer (A) is a divalent metal-containing ethylenically unsaturated monomer (a1) in an amount of 1% by weight to 40% by weight. 0 to 8 wt% of a carboxyl group-containing ethylenically unsaturated monomer (a2), 0 to 40 wt% of a hydroxyl group-containing ethylenically unsaturated monomer (a3), and 99 to 22% by weight of other ethylenically unsaturated monomer (a4) A polymer obtained by solution polymerization in a plurality of stages of two or more stages.

[Ethylenically unsaturated monomer containing divalent metal (a1)]

The amount of the divalent metal-containing ethylenically unsaturated monomer (a1) used as one of the raw materials in the preparation of the above polymer (A) is (a1) to use as a raw material of the polymer (A). The total amount of (a4) is 100% by weight, and is set to be in the range of 1% by weight to 40% by weight. The reason for this is that by setting the amount of the divalent metal-containing ethylenically unsaturated monomer (a1) to 1% by weight or more, it is possible to impart more excellent self-polishing property to the formed coating film. The amount of the divalent metal-containing ethylenically unsaturated monomer (a1) is preferably 5% by weight or more, more preferably 10% by weight or more. In addition, by setting the amount of the divalent metal-containing ethylenically unsaturated monomer (a1) to 40% by weight or less, the balance between adhesion and hydrolysis property is excellent, and long-term self-polishing property is maintained, and the antifouling effect is further improved. improve. The amount of the divalent metal-containing ethylenically unsaturated monomer (a1) is preferably 25 wt% or less, more preferably 20 wt% or less.

The divalent metal-containing ethylenically unsaturated monomer (a1) is a monomer having a carboxyl group ionically bonded to a divalent metal, preferably a divalent metal-containing ethylenically unsaturated having two unsaturated groups. The monomer (a1a) and/or the divalent metal-containing ethylenically unsaturated monomer (a1b) represented by the following formula (I).

CH ₂ =C(R ¹ )-COO-MR ² (I)

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

From the viewpoint of solubility in water, the metal of the divalent metal contained in the divalent metal-containing ethylenically unsaturated monomer (a1) is preferably selected from the group consisting of Mg, Ca, Zn, and Cu. At least one metal in the group consisting of. From the viewpoint of the transparency of the obtained polymer (A), Mg, Ca, Zn, and more preferably Zn are more preferable. One type of the above metals may be used, or two or more types may be used in combination.

Examples of the monomer (a1a) include magnesium acrylate [(CH ₂ =CHCOO) ₂ Mg], magnesium methacrylate [(CH ₂ =C(CH ₃ )COO) ₂ Mg], calcium acrylate [(CH ₂ =CHCOO) ₂ Ca], calcium methacrylate [(CH ₂ =C(CH ₃ )COO) ₂ Ca], zinc acrylate [(CH ₂ =CHCOO) ₂ Zn], zinc methacrylate [(CH ₂ =C(CH) ₃ ) CO2) ₂ Zn], copper acrylate [(CH ₂ =CHCOO) ₂ Cu], copper methacrylate [(CH ₂ =C(CH ₃ )COO) ₂ Cu], etc. salt. The above monomer (a1a) may be appropriately selected from one type or two or more types as needed. Among them, when zinc (meth)acrylate is used, the transparency of the polymer (A) obtained by solution polymerization tends to be high, and the color tone of the coating film of the antifouling paint tends to be beautiful, which is preferable. In addition, "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid".

The monomer (a1a) is obtained by a method of dispersing an inorganic metal compound and a carboxyl group-containing ethylenically unsaturated monomer (for example, acrylic acid or methacrylic acid) in an organic solvent or the like, or having a polymerizable unsaturated group. The reaction is carried out in a reactive diluent. Since the reactant containing the monomer (a1a) component obtained by the above method is excellent in compatibility with an organic solvent or another monomer, polymerization can be easily carried out, which is preferable. The above reaction is preferably carried out in the presence of water, and it is preferred to set the content of water in the reactant to be in the range of 0.01% by weight to 30% by weight.

The organic acid residue of R ² of the above monomer (a1b) may, for example, be monochloroacetic acid, monofluoroacetic acid, acetic acid, propionic acid, octanoic acid, versatic acid, isostearic acid or palmitic acid (palmitic). Acid), Cresotic acid, α-naphthoic acid, β-naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinoline A residue derived from a monovalent organic acid such as carboxylic acid, nitrobenzoic acid, nitronaphthoic acid or pulvic acid. The residue may be appropriately selected as needed, and from the viewpoint of obtaining a highly durable coating film capable of preventing cracking or peeling for a long period of time, a fatty acid (aliphatic monocarboxylic acid)-based residue such as carbon number is preferred. It is a fatty acid residue of 1-20. Further, the organic acid residue of R ² in the above formula (I) means a residual portion from which a proton is removed from a carboxyl group of an organic acid, and is ion-bonded to the metal M instead of the proton.

Specific examples of the monomer (a1b) include magnesium mono(methyl)acetate, calcium (meth)acrylate, zinc (meth)acrylate, and copper (meth)acrylate. ; magnesium mono(methyl) acrylate, calcium (meth) acrylate, zinc (meth) acrylate, copper (meth) acrylate; magnesium (meth) acrylate, acetic acid Calcium (meth) acrylate, zinc (meth) acrylate, copper (meth) acrylate; magnesium (meth) acrylate, calcium (meth) acrylate, zinc (meth) acrylate, Copper (meth)acrylate; magnesium (meth)acrylate, calcium (meth)acrylate, zinc octanoate (meth)acrylate, copper octanoate; magnesium keto acid , kohe acid (meth) acrylate, kehic acid (meth) acrylate, keh acid (meth) acrylate; isostearic acid (meth) acrylate, isostearic acid (methyl) Calcium acrylate, zinc isostearate (meth) acrylate, copper (meth) acrylate, calcium palmitate (meth) acrylate, calcium palmitate (meth) acrylate, brown Zinc acid (meth) acrylate, copper (meth) acrylate; magnesium cresine (meth) acrylate, calcium cresyl (meth) acrylate, zinc cresyl formate (methyl) acrylate, cresol Copper (meth)acrylate; α-naphthoic acid (meth) acrylate, α-naphthoic acid (meth) acrylate, α-naphthoic acid (meth) acrylate, α-naphthoic acid (meth) acrylate ; β-naphthoic acid magnesium (meth) acrylate, β-naphthoic acid (meth) acrylate, zinc β-naphthic acid (meth) acrylate, β-naphthoic acid (meth) acrylate; benzoic acid (methyl Magnesium acrylate, calcium (meth) acrylate, zinc (meth) acrylate, copper (meth) acrylate; magnesium 2,4,5-trichlorophenoxyacetate , 2,4,5-trichlorophenoxyacetic acid (meth) acrylate, 2,4,5-trichlorophenoxyacetic acid (meth) acrylate, 2,4,5-trichlorophenoxy Copper (meth)acrylate; magnesium (meth)acrylate, 2,4-dichlorophenoxyacetic acid (meth)acrylate, 2,4-dichlorophenoxy Zinc acetate (meth) acrylate, 2,4-dichlorophenoxyacetic acid (meth) acrylate Quinolinic acid magnesium (meth) acrylate, quinoline carboxylic acid (meth) acrylate, quinoline carboxylic acid (meth) acrylate, quinoline carboxylic acid (meth) acrylate, nitrobenzoic acid (A) , magnesium acrylate, calcium methacrylate, zinc methacrylate, zinc methacrylate Calcium naphthoate (meth) acrylate, zinc nitronaphthoate (meth) acrylate, copper nitro naphthoate (meth) acrylate; magnesium prasinate (meth) acrylate, prion acid (methyl Calcium acrylate, zinc (meth) acrylate, copper (meth) acrylate, and the like. These monomers (a1b) may be appropriately selected from one type or two or more types as needed. Among them, when a zinc-containing monomer is used, the transparency of the obtained resin component becomes high, and the color tone of the coating film becomes beautiful, which is preferable. Further, from the viewpoint of durability of the coating film, it is more preferable to use a fatty acid (meth)acrylic acid (M of the formula (I) is zinc and R ² is a fatty acid residue). In addition, "(meth)acrylate" means "acrylic acid salt" or "methacrylic acid salt".

The monomer (a1b) is obtained by an inorganic metal compound, a carboxyl group-containing ethylenically unsaturated monomer, and a non-polymerizable organic acid corresponding to the organic acid residue R ² in the formula (I). It is reacted in a diluent such as an organic solvent or a reactive diluent having a polymerizable unsaturated group or the like.

The divalent metal-containing ethylenically unsaturated monomer (a1) is preferably used in combination with the above viewpoint of maintaining the self-polishing property of the formed coating film and sufficiently consuming the coating film to obtain good antifouling properties. Monomer (a1a) and monomer (a1b). Particularly, preferred is zinc (meth)acrylate as the monomer (a1a) and zinc (meth)acrylate as the monomer (a1b) (M of the formula (I) is zinc, and R ² is a fatty acid residue. )The combination.

Further, when the monomer (a1a) and the monomer (a1b) are used in combination as the divalent metal-containing ethylenically unsaturated monomer (a1), it is preferred to use the monomer (a1a) and the monomer (a1b). The ear ratio (a1a/a1b) is set to a range of 10/90 to 90/10. By setting (a1a/a1b) to 90/10 or less, a coating film which is more excellent in crack resistance or adhesion can be obtained, which is preferable. Further, by setting (a1a/a1b) to 10/90 or more, it is possible to maintain sufficient self-polishing property of the formed coating film for a longer period of time, which is preferable. (a1a/a1b) is more preferably in the range of 20/80 to 80/20, and still more preferably in the range of 30/70 to 70/30.

Further, a monomer mixture containing a monomer (a1a) and a monomer (a1b) can be obtained by: an inorganic metal compound, a carboxyl group-containing ethylenically unsaturated monomer, and an organic compound of the formula (I) The non-polymerizable organic acid corresponding to the acid residue R ² is reacted with a diluent such as an organic solvent or a reactive diluent having a polymerizable unsaturated group or the like.

In this case, it is preferred to set the amount of the non-polymerizable organic acid to be 0.01 to 3 moles per mole of the inorganic metal compound, and more preferably 0.01 to 0 to 0.95 times. The scope of Moore. When the amount of use of the non-polymerizable organic acid is set to 0.01 times or more, the solid deposition in the monomer mixture production step can be suppressed, and the self-polishing property and the crack resistance of the coating film are further improved. better. In addition, when the amount of use of the non-polymerizable organic acid is set to 3 times or less, the antifouling property of the coating film can be maintained for a longer period of time, which is preferable. More preferably, the non-polymerizable organic acid is used in an amount of from 0.1 to 0 times moles.

Further, as described later, even when the divalent metal-containing ethylenically unsaturated monomer (a1) is not used in the raw material when the polymer (A) is synthesized, the following (i) can be carried out in that order. To (iii), the unit corresponding to (a1) is contained in the polymer (A).

(i) The first stage polymerization is carried out using the monomer mixture (b1) containing the carboxyl group-containing ethylenically unsaturated monomer (a2) as a raw material of the first stage.

(ii) reacting the polymer obtained in the first stage with a divalent metal compound, thereby introducing a divalent metal into the polymer of the first stage.

(iii) The second-stage polymerization is carried out by using a monomer mixture (b3) containing a carboxyl group-containing ethylenically unsaturated monomer (a2) as a raw material of the second stage in the presence of the above reactant.

[Carboxyl group-containing ethylenically unsaturated monomer (a2)]

The amount of the carboxyl group-containing ethylenically unsaturated monomer (a2) used as one of the raw materials in the preparation of the above polymer (A) is (a1) to (a4) used as a raw material of the polymer (A). The total amount of 100% by weight is set to be in the range of 0 to 8 wt%. The amount of the carboxyl group-containing ethylenically unsaturated monomer (a2) is preferably 1% by weight or more, more preferably 2% by weight or more, from the viewpoint that the storage stability becomes good. In addition, when the amount of the carboxyl group-containing ethylenically unsaturated monomer (a2) exceeds 8 wt%, the viscosity of the polymer becomes extremely high, and the water resistance and adhesion of the coating film are lowered. The amount of the carboxyl group-containing ethylenically unsaturated monomer (a2) is preferably 7% by weight or less, more preferably 6% by weight or less. Further, the carboxyl group-containing ethylenically unsaturated monomer (a2) is an optional component.

The carboxyl group-containing ethylenically unsaturated monomer (a2) may, for example, be methacrylic acid, acrylic acid, crotonic acid, vinyl benzoic acid, fumaric acid, itaconic acid, maleic acid, a monobasic or dibasic acid monomer such as citraconic acid, monomethyl maleate, monoethyl maleate, monobutyl maleate, Monooctyl maleate, monomethyl iconate, monoethyl iconate, monobutyl itaconate, mono-octyl iconate, monomethyl fumarate, anti-butene Acid monoethyl ester, monobutyl methacrylate, monooctyl fumarate, monoethyl maleic acid, hydroxyethyl mono(meth)acrylate (tetraethyl methacrylate) Tetrahydrophthalic acid monohydroxyethyl(meth)acrylate), hydroxypropyl mono(meth) acrylate, hydroxybutyl methacrylate monobutyl phthalate, mono(methyl) phthalate Hydroxyethyl acrylate, hydroxypropyl mono(meth)acrylate, succinic acid monohydroxyethyl(meth)acrylate Dibasic acid or anhydride represented by hydroxypropyl mono(meth)acrylate, hydroxyethyl maleic acid mono(meth)acrylate, hydroxypropyl maleic acid mono(meth)acrylate Monoester monoesters and the like. One or two or more of these monomers may be appropriately selected as needed.

[Hydroxy group-containing ethylenically unsaturated monomer (a3)]

The amount of the hydroxyl group-containing ethylenically unsaturated monomer (a3) used as one of the raw materials in the preparation of the polymer (A) is (a1) to (a1) used as a raw material of the polymer (A). The total amount of a4) is 100% by weight, and is set to a range of 0 to 40% by weight. The hydroxyl group-containing ethylenically unsaturated monomer (a3) is an optional component, but when it is set to 40% by weight or less, the water resistance of the coating film is improved and the adhesion tends to be good. The amount of the hydroxyl group-containing ethylenically unsaturated monomer (a3) is more preferably 30% by weight or less, still more preferably 20% by weight or less.

Examples of the hydroxyl group-containing ethylenically unsaturated monomer (a3) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. a hydroxyl group-containing (meth) acrylate monomer such as 2-hydroxybutyl acrylate or 4-hydroxybutyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate with ethylene oxide, propylene oxide, An adduct of γ-butyrolactone or ε-caprolactone; a dimer or a trimer of 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; glycerin ( a monomer having a plurality of hydroxyl groups such as methyl acrylate; ethylene glycol allyl ether, propylene glycol allyl ether, polyethylene glycol allyl ether, polypropylene glycol allyl ether, polyethylene glycol-polypropylene glycol allyl a terminal hydroxyallylized polyether monomer such as ether. One or two or more of these monomers may be appropriately selected as needed.

[Other ethylenically unsaturated monomer units (a4)]

The amount of the other ethylenically unsaturated monomer (a4) used as one of the raw materials in the preparation of the above polymer (A) is (a1) to (a4) used as a raw material of the polymer (A). The total amount is 100% by weight and is set to a range of 99% by weight to 22% by weight.

The other ethylenically unsaturated monomer (a4) is as long as it is a divalent metal-containing ethylenically unsaturated monomer (a1), a carboxyl group-containing ethylenically unsaturated monomer (a2), and a hydroxyl group-containing ethylenically unsaturated monomer. The monomer having a polymerizable (C=C) double bond different in the body (a3) is not particularly limited. The polymer (A) contains a unit derived from another ethylenically unsaturated monomer (a4), whereby the flexibility of the formed coating film, the crack resistance, the peeling resistance, and the long-term self-abrasive property can be balanced. Preferably, these characteristics are good.

Examples of the other ethylenically unsaturated monomer (a4) include methyl (meth)acrylate, ethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, and 2-ethyl (meth)acrylate. Oxyethyl ester, 2-butoxyethyl (meth)acrylate, butoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxy polymerization Ethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, 2-(2-ethylhexyloxy)ethyl (meth) acrylate, 1-methyl (meth) acrylate 2-methoxyethyl ester, 3-methoxybutyl (meth)acrylate, 3-methyl-3-methoxybutyl (meth)acrylate, m-methoxyphenyl (meth)acrylate , p-methoxyphenyl (meth)acrylate, o-methoxyphenylethyl (meth)acrylate, m-methoxyphenylethyl (meth)acrylate, p-methoxy (meth)acrylate Phenylethyl ester, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylate (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, (a) (meth) acrylate monomer such as cyclohexyl acrylate, glycidyl (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctyl (meth) acrylate; (methyl) Ethylene monomer containing primary and secondary amine groups such as butylaminoethyl acrylate or (meth) acrylamide; dimethylaminoethyl (meth) acrylate, diethyl (meth) acrylate Aminoethyl ester, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, dimethylamino B a tertiary amino group-containing ethylene monomer such as a (meth) acrylamide or a dimethylaminopropyl (meth) acrylamide; a vinyl pyrrolidone, a vinyl pyridine, a vinyl carbazole a heterocyclic basic monomer; a vinyl monomer such as styrene, vinyl toluene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate or vinyl propionate; Oxypoly polyethylene glycol allyl ether, methoxy polypropylene glycol allyl ether, butoxy polyethylene glycol allyl ether, butoxy polypropylene glycol allyl ether, methoxy polyethylene glycol-polypropylene glycol Terminal alkoxyallyylated polyether monomer such as propyl ether, butoxy polyethylene glycol-polypropylene glycol allyl ether; ethylene glycol di(meth)acrylate, diethylene glycol di(methyl) Acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, allyl methacrylate, triallyl cyanurate, cis A polyfunctional monomer such as diallyl butenate or polypropylene glycol diallyl ether. These monomers may be appropriately selected to use one type or two or more types as needed.

Further, a reactive emulsifier may be used as the other ethylenically unsaturated monomer (a4) which functions as an emulsifier during the polymerization reaction and copolymerizes with the monomer to form the obtained copolymer. Structural units. When a reactive emulsifier is introduced into the polymer (A), the unit derived from the reactive emulsifier contributes to an improvement in dispersibility.

As such a reactive emulsifier, a surfactant having a radically polymerizable intercarbon double bond (C=C) can be used, and preferably, a carbon-to-carbon double bond having a radical polymerizable property (C=C) can be used. A nonionic surfactant or an anionic surfactant.

Further, such a reactive emulsifier is, for example, "Antox MS60" manufactured by Japan Emulsifier Co., Ltd., "Aqualon HS-05" manufactured by First Industrial Pharmaceutical Co., Ltd., "Aqualon HS-10", and "Aqualon HS-20". "Adeka Reasoap SE10", "Adeka Reasoap SR10" and "Adeka Reasoap SR20" manufactured by ADEKA, an anionic reactive emulsifier such as "Eleminol JS2" manufactured by Sanyo Chemical Industries Co., Ltd.; "Aqualon" manufactured by Daiichi Kogyo Co., Ltd. RN-10", "Aqualon RN-20", "Aqualon RN-30", non-ionics such as "Adeka Reasoap NE10", "Adeka Reasoap NE20", "Adeka Reasoap NE30", "Adeka Reasoap ER10" manufactured by ADEKA A reactive emulsifier. These reactive emulsifiers may be appropriately selected from one type or two or more types as needed.

Further, in the hydroxyl group-containing ethylenically unsaturated monomer (a3) or other ethylenically unsaturated monomer (a4), the allylic acid lacking radical polymerization property can be compared with the (meth) acrylate monomer. The base polyether monomer is used as a reactive diluent in the synthesis of the polymer (A) when the divalent metal-containing ethylenically unsaturated monomer (a1) is synthesized. When synthesizing the divalent metal-containing ethylenically unsaturated monomer (a1) or the polymer (A), it is necessary to introduce a diluent such as an organic solvent into the reaction vessel as a reaction medium, by using the above ally The use of the polyether monomer as a part or all of the organic solvent can reduce the amount of the necessary organic solvent and, in addition, improve the storage stability.

[Polymer (A)]

The polymer (A) contained in the resin dispersion for an antifouling coating produced by the method of the present invention is synthesized by polymerizing the above (a1) to (a4) monomers in two or more stages.

The above polymer (A) is obtained by first using a part of the monomers (a1) to (a4) used as a raw material in a diluent for dissolving the polymer (A) in a polymerization initiator. The first stage of polymerization is carried out in the presence of the catalyst, and thereafter, the remainder of the above (a1) to (a4) monomers is subjected to polymerization after the second stage.

From the viewpoint of storage stability of the polymer, the above polymer (A) is preferably obtained by a step of performing solution polymerization in a plurality of stages including two or more stages of the following steps: bringing at least one carboxyl group-containing ethylene a step of performing solution polymerization of the monomer mixture (b1) of the unsaturated monomer (a2); and an ethylenically unsaturated monomer containing no carboxyl group-containing ethylenically unsaturated monomer (a2) and containing a divalent metal The monomer mixture (b2) of the body (a1) is subjected to a solution polymerization step. (a1) is preferably (a1a) or (a1b). It is generally presumed that by using such a multistage polymerization method, a carboxyl group can be locally introduced into the polymer, whereby dispersion stability and water resistance of the coating film are improved, and the viscosity at the time of preparation of the aqueous dispersion can be lowered.

The polymerization order of the monomer mixture (b1) and (b2) is not limited, and in terms of the excellent dispersion stability of the polymer over time, it is preferred to polymerize the monomer mixture (b1) and then (b2). When the monomer mixture (b2) is first polymerized and then the monomer mixture (b1) is polymerized, a part of the formed metal ester moiety may be dissociated by transesterification by the action of a carboxyl group, and the stability is lowered.

Further, the above polymer (A) can be obtained by a multistage polymerization comprising at least the following steps: solution polymerization of a monomer mixture (b1) containing at least one carboxyl group-containing ethylenically unsaturated monomer (a2) a first stage polymerization; a step of reacting the polymer obtained in the first stage polymerization with a divalent metal compound; and, in the presence of the reactant of the above step, an ethylenically unsaturated monomer containing at least one carboxyl group ( The monomer mixture (b3) of a2) is subjected to a second-stage polymerization of the polymerization.

According to this method, even when the divalent metal-containing ethylenically unsaturated monomer (a1) is not used in the raw material, the carboxyl group of the polymer obtained in the first-stage polymerization can be reacted with the divalent metal compound. Further, a unit of the divalent metal-containing ethylenically unsaturated monomer (a1) is introduced into the polymer.

The method of adding a metal to the carboxy group of the polymer obtained in the first-stage polymerization can be carried out, for example, according to a known method described in JP-A-62-57464 or JP-A-8-209005. Specifically, the polymer obtained in the first-stage polymerization, an oxide of a divalent metal, a hydroxide of a divalent metal or a chloride of a divalent metal, and a monovalent organic acid or water may be used in the polymerization. It is carried out by heating and stirring at a temperature lower than the decomposition temperature or decomposition temperature of the substance.

The diluent used in the above polymerization reaction is not particularly limited, and specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-butanol, and 2- Monohydric alcohols such as methoxyethanol and 3-methyl-3-methoxybutanol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, 2 -methyl-2,4-pentanediol, 2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin Polyols such as acetone, methyl ethyl ketone, ketones such as acetamidine acetone, ethers such as methyl ethyl ether and dioxane, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monohexyl ether , ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol mono-tert-butyl ether, ethylene Alcohol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol II Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-iso Butyl ether, diethylene glycol mono-tert-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol monoisobutyl Ether, dipropylene glycol mono-tert-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether , glycol ethers such as tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, triethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate Ester, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol monoisopropyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethyl Glycol monoacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether a glycolic acid ester such as an ester; an aliphatic hydrocarbon such as n-pentane or n-hexane; an aromatic hydrocarbon such as toluene, xylene or solvent naphtha; and the above allylated polyether body. These diluents may be used alone or in combination of two or more. However, it is preferred to contain an alcohol compound because the production stability and water dispersion stability of the polymer (A) are good. From the viewpoint of reducing the amount of the organic solvent, the diluent in the first-stage polymerization described above is preferably an allylated polyether monomer.

The polymerization initiator is not particularly limited, and a known polymerization initiator can be used. For example, t-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, laurel peroxide, benzammonium peroxide, peroctanoic acid Organic suitable oxides such as t-butyl peroctoate, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylbutyronitrile) An azo compound such as (Azobismethylbutyronitrile, AMBN). The polymerization initiator may be used alone or in combination of two or more. The amount of the polymerization initiator to be used is not particularly limited, and can be appropriately set.

Further, a known chain transfer agent may be used in the above polymerization reaction as needed.

The molecular weight of the polymer (A) obtained as described above can be appropriately determined depending on the desired properties, and can be set, for example, in the range of from 1,000 to 50,000 by weight average molecular weight (Mw).

[Resin dispersion for antifouling coating]

The resin dispersion for an antifouling coating of the present invention can be obtained by dispersing the polymer (A) obtained in the above manner in a dispersion medium containing water or a water/organic solvent mixture.

With respect to the above polymer (A), from the viewpoint of smooth movement of the aqueous phase, it is preferred to use at least a carboxyl group-containing ethyl group in the presence or absence of a diluent for dissolving the polymer (A). The saturated monomer (a2) is solution-polymerized, and then a part or all of the carboxyl group in the obtained polymer is neutralized, and then dispersed in the above dispersion medium. The above neutralization is carried out by adding a basic compound to the polymer (A). The basic compound to be used is not particularly limited, and examples thereof include ammonia (aqueous solution), alkylamines such as trimethylamine, triethylamine, diisopropylethylamine and butylamine, and dimethyl groups. Alcoholamines such as ethanolamine, dimethylisopropanolamine, methyldiethanolamine, diethylethanolamine, triethanolamine, butanolamine, morpholine, isophorone diamine, and the like. The basic compound may be used alone or in combination of two or more. The above basic compound is added in such a manner that the degree of neutralization (i.e., the molar ratio of the neutralizing agent to the acid) is from 40% to 150%, preferably from 60% to 120%. The resin dispersion for an antifouling coating of the present invention has a pH of from 6.0 to 11.0, preferably from 6.5 to 9.0.

Further, in the above polymer (A), at least a hydroxyl group-containing ethylenically unsaturated monomer (a3) is used for solution polymerization, and the polymer (A) is dispersed in the above dispersion medium, and then a hydroxyl functional group is further added. Crosslinking is carried out by a crosslinking agent, whereby the coating film properties such as toughness and water resistance are improved, which is preferable.

The hydroxy functional crosslinking agent is not particularly limited, and a known hydroxy functional crosslinking agent can be used. For example, an amine-based resin such as a melamine resin or a benzoguanamine resin, a polyisocyanate such as an aliphatic isocyanate, an alicyclic isocyanate or an aromatic isocyanate may be mentioned. Particularly, from the viewpoints of the reaction temperature and the physical properties of the coating film, it is preferred to use a polyisocyanate, and it is more preferred to use a water-soluble or water-dispersible hydroxy-functional crosslinking agent.

The amount of the hydroxy-functional crosslinking agent to be used is not particularly limited, and can be used in a range in which operability, film forming properties, and antifouling properties are not lowered.

The resin dispersion for an antifouling coating preferably contains the polymer (A) in the range of 20% by weight to 60% by weight in terms of film forming property and antifouling property.

The above dispersion medium may use water or a water/organic solvent mixture. As the above organic solvent, a diluent used in the polymerization of the polymer (A) can be used. In terms of dispersibility, the diluent is preferably an alcohol compound such as an alcohol or a glycol ether exemplified as the diluent used in the polymerization reaction. Among these compounds, the alcohol may preferably be a monohydric alcohol having a relatively low boiling point of from 1 to 6, preferably from 2 to 4 carbon atoms, and a glycol ether preferably having a carbon number of from 3 to 3. 11. A glycol ether having a carbon number of 3 to 8 is preferred.

The content of the above diluent in the resin dispersion for an antifouling coating is preferably from 0 to 20% by weight, more preferably from 0 to 10% by weight. When the content of the diluent exceeds the above range due to the diluent used in the polymerization reaction of the polymer (A), it is necessary to reduce the content of the diluent, and if necessary, the removal of the diluent may be carried out by vacuum distillation or the like. (desolvent treatment).

Further, other antifouling agents may be blended in the resin dispersion for an antifouling coating of the present invention as needed. The antifouling agent can be appropriately selected and used according to the desired properties, and examples thereof include copper antifouling agents such as cuprous oxide, cuprous thiocyanate, and copper powder, and lead, zinc, nickel, and the like. A compound of another metal, an amine derivative such as diphenylamine, a nitrile compound, a benzothiazole compound, a maleimide compound, a pyridine compound or the like. These antifouling agents may be used alone or in combination of two or more. More specifically, it can be exemplified by manganese ethylene bis (dithiocarbamate), zinc dimethyl dithiocarbamate, 2-methylthio-4. -T-butylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloro Benzonitrile (2,4,5,6-tetrachloroisophthalonitrile), N,N-dimethyldichlorophenylurea, zinc ethyl bis(dithiocarbamic acid), copper thiocyanate , 4,5-dichloro-2-n-octyl-3(2H)isohydrothiazolone (4,5-dichloro-2-n-octyl-3(2H)-isothiazolone), N-(fluorodi Chloromethylthio)phthalimide, N,N'-dimethyl-N'-phenyl-(N-fluorodichloromethylsulfonyl)sulfonamide (N,N'-dimethyl-N '-benzyl-(N-fluorodichloromethylthio)sulfa mide), 2-pyridinethiol-1-oxide zinc salt, tetramethylthiuram sulfide, Cu-10%Ni solid solution alloy, 2,4,6-trichlorophenyl maleimide, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, 3 -iodo-2-propynylbutylamino group 3-iodo-2-propenylbutylcarbamate, diiodomethyl-p-tolyl sulfone, bis(dimethyldithiocarbamyl)exyl bis(dithioamine) Bis(dimethyldithiocarbamoyl)zinc ethylenebis(dithiocarbamate), phenyl(bispyridyl)bismuth dichloride, 2-(4-thiazolyl)-benzimidazole (2) -(4-thiazolyl)-benzimidazole), pyridine-triphenylborane, and the like.

In the resin dispersion for an antifouling coating of the present invention, dimethyl siloxane, silicone oil, or the like may be blended for the purpose of imparting lubricity to the surface of the coating film and preventing bio-adhesion. A fluorine-containing compound such as a ruthenium compound or a fluorinated carbon.

Further, the resin dispersion for an antifouling coating of the present invention may contain various pigments, antifoaming agents, pigment dispersing agents, flow leveling agents, anti-sagging agents, matting agents, ultraviolet absorbers, antioxidants, heat resistance enhancers, and assistance. A lubricant, a preservative, a plasticizer, other emulsion resins, a water-soluble resin, a viscosity control agent, and the like.

The coating film using the resin dispersion for an antifouling coating of the present invention can be formed directly or through a primer film on water structures such as ships or various fishing nets, harbor facilities, oil fences, bridges, and seabed bases. The surface of the substrate. The undercoat film can be formed using a primer such as a wash primer, a chlorinated rubber or an epoxy, or an intermediate coat. Regarding the method for forming a coating film, the resin dispersion for an antifouling coating of the present invention can be applied onto a substrate surface or a substrate by a method such as brush coating, spray coating, roll coating, or immersion coating. The bottom layer is coated on the film. The coating amount can be usually set to a thickness in which the dried coating film reaches a thickness of from 10 μm to 400 μm. The drying of the coating film can usually be carried out at room temperature, and if necessary, it can be dried by heating.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited by the examples. Further, the parts in the examples represent parts by weight. The evaluation of the resin dispersion for an antifouling coating prepared in the present example was carried out by the method shown below.

[Storage Stability Evaluation]

In the evaluation of the storage stability of the resin dispersion for an antifouling coating, the resin dispersion for an antifouling coating was stored at a temperature of 40 ° C for 3 days, 10 days, and 1 month, and the presence or absence of the precipitate was visually confirmed. The evaluation was carried out in accordance with the following criteria.

○: The resin component did not precipitate after a certain period of time. ‧ Separation did not form a coagulum

△: There is a small amount of precipitate, but the precipitate is dispersed by stirring.

X: The resin component was precipitated and separated, and solidified, and was not dispersed again even after stirring.

[Measurement of consumption of film]

Using a applicator, the resin dispersion for an antifouling coating was applied to a hard vinyl chloride plate of 50 mm × 50 mm × 2 mm (thickness) so as to have a dry film thickness of 120 μm to prepare a test plate, and the test plate was prepared. It was installed in a rotary drum set in seawater and rotated at a peripheral speed of 7.7 m/s (15 knot) to measure the film thickness after one month and three months.

[Water resistance test]

A test plate was prepared by applying a resin dispersion for an antifouling coating to a substrate containing a blast-coated steel sheet to which a rust-preventive coating was applied in advance so that the dried film thickness was 120 μm. After the test plate was immersed in sterile filtered seawater for one month, the test plate was dried at room temperature of 20 ° C for one week, and the surface of the coating film was observed. The evaluation was carried out in accordance with the following criteria.

◎: Crack and peeling were not observed at all

○: A little crack was observed.

△: Cracks and peeling were observed in a part of the surface of the coating film.

×: Cracks and peeling were observed in the entire surface of the coating film.

[Grid stripping test]

The test plate prepared in the same manner as the above water resistance test was immersed in the sterilized filtered seawater for one month, and then the test plate was dried at room temperature of 20 ° C for one week to carry out a mesh peeling test. In the mesh peeling test, cross-cutting of the test piece to the substrate was performed at intervals of 2 mm, and 25 grids of 2 mm ² were produced, and Sellotape (registered trademark) was attached thereto and sharply peeled off. , observe the state of the stripped mesh. The evaluation was carried out in accordance with the following criteria.

◎: The peeling of the mesh and the peeling of the corners of the mesh were not observed at all.

○: The mesh is not peeled off, but only the corners of the mesh are peeled off

△: 1 to 12 mesh stripping

×: 13 to 25 mesh strips.

[Manufacturing example M1]

In a reaction vessel equipped with a stirrer, a temperature adjuster, and a dropping device, 66.3 parts of MFDG (dipropylene glycol monomethyl ether) and 41 parts of zinc oxide (ZnO) were added, and the temperature was raised to 75 ° C while stirring. Thereto, a mixture containing the following raw materials was added dropwise at a constant rate over 3 hours.

43 parts of methacrylic acid (MAA)

Acrylic acid (AA) 36 parts

5 parts of water

After the completion of the dropwise addition, the reaction solution was changed from a milky white state to a transparent state. After further stirring for 2 hours, 10 parts of MFDG was added to obtain a transparent divalent metal-containing ethylenically unsaturated monomer mixture M1. The amount of each raw material added, the metal content of the obtained divalent metal-containing ethylenically unsaturated monomer mixture M1, and the solid content concentration are shown in Table 1.

[Production Example M2, Production Example M3]

The divalent metal-containing ethylenically unsaturated monomer mixture M2 and the divalent metal-containing ethylenically unsaturated monomer mixture M3 were produced in the same manner as in Production Example M1 in the amounts shown in Table 1. In place of MFDG, PKA5001 was used in Production Example M2, and AG was used in Production Example M3.

[Manufacturing example P1]

In a reaction vessel equipped with a stirrer, a temperature adjuster, and a dropping device, 25.9 parts of MFDG (dipropylene glycol monomethyl ether) was added, and the temperature was raised to 130 ° C while stirring.

<Step 1>

Thereafter, a mixture containing the following raw materials was dropwise added at a constant rate for 1 hour, and further, a copolymerization reaction was carried out for 0.5 hours (hereinafter, this reaction step is referred to as Step 1).

Acrylic (AA) 1 part

14 parts of ethyl acrylate (EA)

Chain transfer agent (trade name: "Nofmer MSD", manufactured by Nippon Oil & Fats Co., Ltd.) 0.5 parts

One part of the starting agent (trade name: "Perbutyl O", manufactured by Nippon Oil & Fats Co., Ltd.).

<Step 2>

Next, a mixture including the following raw materials was added dropwise at a constant rate over 3 hours, and further, a copolymerization reaction was carried out for 0.5 hours (hereinafter, this reaction step is referred to as Step 2).

M1 9.1 parts of a divalent metal-containing ethylenically unsaturated monomer mixture (5 parts of a divalent metal-containing ethylenically unsaturated monomer)

25 parts of methyl methacrylate (MMA)

Ethyl acrylate (EA) 45 parts

10 parts of n-butyl acrylate (BA)

Chain transfer agent (trade name: "Nofmer MSD", manufactured by Nippon Oil & Fats Co., Ltd.) 1 part

Starting agent (trade name: "Perbutyl O", manufactured by Nippon Oil & Fats Co., Ltd.) 5 parts.

Next, 0.5 part of "Perbutyl O" was added, and the polymerization reaction was continued for 1 hour. Further, the temperature was lowered to 80 ° C, 1.1 parts of dimethylethanolamine (DMEA) was added, and the mixture was mixed until homogeneous, and then 92.2 parts of deionized water was slowly added to obtain a polymer (A) aqueous dispersion P1. The amount of each raw material added, the characteristic value of the polymer (A) aqueous dispersion P1, and the storage stability are shown in Table 2.

[Production Example P2 to Production Example P12]

The polymer (A) aqueous dispersion P2 to the polymer (A) aqueous dispersion P12 were produced in the same manner as in Production Example P1 in the amounts shown in Table 2.

In the production example P7, after the completion of the step 1, 7.1 parts of zinc hydroxide and 7 parts of koco acid were added and stirred for 2 hours, and then the step 2 was continued. The amount of the divalent metal-containing ethylenically unsaturated monomer (a1) used in Production Example P7 was calculated in the following manner.

Molecular weight obtained by removing hydrogen atoms from AA: 71

Molecular weight obtained by removing hydrogen atoms from kocholic acid: 174

Formula weight of zinc hydroxide: 99.4

Amount of zinc atom: 65.4

Part AA: 7.6 x 71/72 = 7.49

Part of zinc hydroxide: 7.1 parts × 65.4 / 99.4 = 4.67 parts

Koch acid part: 7 parts × 174 / 175 = 6.96 parts

7.49+4.67+6.96=19.12.

Furthermore, in the production example P8, after the same procedure as in the production example P1, 7 parts of a hydroxy-functional crosslinking agent (trade name: "Bayhydur VPLS2336", manufactured by Bayer Co., Ltd.) was further added, and stirring was continued for 2 hours in this state. A polymer (A) aqueous dispersion P8 was obtained.

Further, in Production Example P10, the monomer mixture containing the carboxyl group-containing ethylenically unsaturated monomer (a2) and the divalent metal-containing ethylenically unsaturated monomer mixture (M1) was carried out without performing step 2. One-stage polymerization.

PKA5006: methoxypolyethylene glycol allyl ether (trade name: "Uniox PKA5006", manufactured by Nippon Oil & Fats Co., Ltd.)

PKA5001: Polyethylene glycol allyl ether (trade name: "Uniox PKA5001", manufactured by Nippon Oil & Fats Co., Ltd.)

AG: Ethylene glycol allyl ether (manufactured by Japan Emulsifier)

SR10: "Adeka Reasoap SR10" (made by Adeka Co., Ltd.) * In parts of the parentheses, only the weight of the monomer component

[Example 1]

To 222.2 parts of the polymer (A) aqueous dispersion P1 obtained in Production Example P1, 30 parts of water was mixed to obtain a resin dispersion for an antifouling coating. Table 3 shows the results of the amount of each raw material and the results of the consumption test of the obtained resin dispersion for antifouling paint, the water resistance test, and the mesh peeling test.

[Example 2 to Example 9]

A resin dispersion for an antifouling coating was prepared and produced in the same manner as in Example 1 except for Production Example P2 to Production Example P9. The results are shown in Table 3.

[Comparative Example 1 to Comparative Example 3]

A resin dispersion for an antifouling coating was prepared and produced in the same manner as in Example 1 except for Production Example P10 to Production Example P12. The results are shown in Table 3.

The storage stability, that is, the dispersion stability of the polymer (A) aqueous dispersion P1 to the polymer (A) aqueous dispersion P9 prepared in Production Example P1 to Production Example P9 was good (Table 2). Further, when stored for one month or more, a part of the precipitate was generated, but the precipitated resin was dispersed by stirring again. In addition, the resin dispersion for antifouling coatings (Examples 1 to 9) using the polymer (A) aqueous dispersion P1 to the polymer (A) aqueous dispersion P9 is excellent in water resistance in seawater and self-polishing property. The adhesion is also good (Table 3).

On the other hand, the polymer (A) aqueous dispersion P10 prepared by performing the polymerization of the monomer mixture in one stage without the step 2 is extremely high (Table 2), and the polymer (A) water is used. The resin dispersion for antifouling coating of the dispersion P10 (Comparative Example 1) had low water resistance and adhesion (Table 3). In addition, the resin dispersion for antifouling coating (Comparative Example 2) of the polymer (A) aqueous dispersion P11 prepared without using the divalent metal-containing ethylenically unsaturated monomer (a1) did not exhibit self-polishing property. (table 3). Further, the viscosity of the resin dispersion for antifouling coating (Comparative Example 3) using the polymer (A) aqueous dispersion P12 using 10% by weight of the carboxyl group-containing ethylenically unsaturated monomer (a2) was extremely high (Table 2). And water resistance and adhesion are low (Table 3).

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Claims (5)

A method for producing a resin dispersion for an antifouling coating, comprising: a step of producing a divalent metal-containing polymer (A); and dispersing the polymer (A) in a dispersion medium containing water or a water/organic solvent mixture The step wherein the divalent metal-containing polymer (A) is 1 wt% to 40 wt% of a divalent metal-containing ethylenically unsaturated monomer (a1), and 1 to 8 wt% of a carboxyl group-containing ethylenically unsaturated monomer The solution (a2), 0 to 40% by weight of the hydroxyl group-containing ethylenically unsaturated monomer (a3), and 99% by weight to 22% by weight of the other ethylenically unsaturated monomer (a4) are subjected to solution polymerization in a plurality of stages of two or more stages. And the obtained polymer; the above polymer (A) is obtained by solution polymerization in two stages of two or more stages including the following steps: a monomer mixture containing at least one carboxyl group-containing ethylenically unsaturated monomer (a2) (b1) a step of performing solution polymerization; and a monomer mixture (b2) containing no carboxyl group-containing ethylenically unsaturated monomer (a2) and containing a divalent metal-containing ethylenically unsaturated monomer (a1) The step of solution polymerization. A method for producing a resin dispersion for an antifouling coating, comprising: a step of producing a divalent metal-containing polymer (A); and dispersing the polymer (A) in a dispersion medium containing water or a water/organic solvent mixture The step wherein the divalent metal-containing polymer (A) is 1 wt% to 40 wt% of a divalent metal-containing ethylenically unsaturated monomer (a1), and 1 to 8 wt% of a carboxyl group Ethylene unsaturated monomer (a2), 0-40% by weight of hydroxyl group-containing ethylenically unsaturated monomer (a3), and 99% by weight to 22% by weight of other ethylenically unsaturated monomer (a4) in two stages or more a polymer obtained by solution polymerization in multiple stages; the above polymer (A) is obtained by multistage solution polymerization comprising at least the following steps: a single sheet containing at least one carboxyl group-containing ethylenically unsaturated monomer (a2) The bulk mixture (b1) is subjected to a first-stage polymerization of solution polymerization; a step of reacting the polymer obtained in the first-stage polymerization with a divalent metal compound; and in the presence of the reactant of the above step, containing at least one The monomer mixture (b3) of the carboxyl group-containing ethylenically unsaturated monomer (a2) is subjected to polymerization in the second stage. The method for producing a resin dispersion for an antifouling coating according to the first or second aspect of the invention, wherein the polymer (A) is in the presence or absence of a diluent for dissolving the polymer (A) After solution polymerization is carried out using at least a carboxyl group-containing ethylenically unsaturated monomer (a2), a part or all of the carboxyl group in the obtained polymer is neutralized, and then dispersed in the dispersion medium. The method for producing a resin dispersion for an antifouling coating according to the first or second aspect of the invention, wherein the polymer (A) is solution-polymerized using at least a hydroxyl group-containing ethylenically unsaturated monomer (a3). After dispersing the polymer (A) in the dispersion medium, a hydroxy-functional crosslinking agent is further added to carry out crosslinking. An antifouling coating, including by claim 1 or A resin dispersion for an antifouling coating produced by the method according to the second aspect.