WO2020235382A1 - Antifouling coating composition - Google Patents

Abstract

Provided is an environmental load-reducing antifouling coating composition, which exhibits antifouling properties over a long period of time even when the amount of an organic antifouling agent is reduced, retains excellent physical properties over a long period of time (for example, the occurrence of cracks is suppressed over a long period of time), and forms an antifouling coating film having excellent drying properties and film strength, the coating film exhibiting suppressed discoloration after becoming deteriorated, and thus having an excellent appearance. Also, provided are: an antifouling coating film formed with the antifouling coating composition; an antifouling coating film-attached substrate; and a method for producing same.　The antifouling coating composition contains: a hydrolyzable polymer (A) containing a metal ester group; a zinc oxide (B); a monocarboxylic acid compound (C) and/or a metal ester thereof; and an organic antifouling agent (D), wherein the content of the zinc oxide (B) in the solid content of the antifouling coating composition is 55-75 mass%, the content of the monocarboxylic acid compound (C) and/or a metal ester thereof in the solid content of the antifouling coating composition is 0.1-10 mass%, and the content of the organic antifouling agent (D) in the solid content of the antifouling coating composition is 10 mass% or less.

Description

Antifouling paint composition

The present invention relates to an antifouling coating composition, an antifouling coating film, a base material with an antifouling coating film using the same, and a method for producing the same.

In the base material of fishery materials such as ships, underwater structures, and fishing nets, the surface of the base material exposed to water for a long period of time includes animals such as oysters, mussels, and wisteria, plants such as seaweed, and bacteria. Various aquatic organisms are easily attached, and in recent years, the activity of marine organisms has increased due to the rise in seawater temperature due to global warming, and the polluted environment has become severe. As a countermeasure, a hydrolyzable antifouling paint is applied. The hydrolyzable antifouling paint is a mechanism in which the surface of the coating film is renewed by hydrolysis to elute the antifouling agent component and exhibit antifouling property.
Patent Document 1 describes an antifouling coating composition capable of forming an antifouling coating having a stable degree of coating wear on ships, underwater structures, etc., and exhibiting excellent antifouling properties over a long period of time. An antifouling coating composition containing a hydrolyzable copolymer (A) and an antifouling agent (B) for the purpose of providing the above-mentioned hydrolyzable copolymer (A). It is at least one hydrolyzable copolymer selected from the group consisting of the metal salt bond-containing copolymer of the above and a specific silyl ester copolymer, and contains at least medetomidine as the antifouling agent (B). The antifouling coating composition characterized by the above is described.
Further, Patent Document 2 contains a metal ester group for the purpose of providing an antifouling coating composition capable of forming an antifouling coating film which maintains high antifouling property for a long period of time and has excellent damage resistance. It contains the hydrolyzable polymer (A), zinc oxide (B), and medetomidine (C), and the content of zinc oxide (B) in the solid content is 27 to 60% by mass. Dirty paint compositions are described.

International Publication No. 2011/118526 International Publication No. 2018/003135

The antifouling coating composition described in the patent document maintains high antifouling property and physical properties for a long period of time by selecting various antifouling agents.
Specifically, Patent Document 1 relates to a technique for exhibiting excellent static antifouling property by combining a hydrolyzable resin such as a metal bond-containing copolymer or a silyl ester copolymer with medetomidine. Further, Patent Document 2 describes that an excellent marine biofouling prevention effect can be obtained by using medetomidine and an algae adhesion inhibitor in combination.
That is, although the above patent document describes the evaluation and effectiveness of antifouling property and physical properties, there is no knowledge about discoloration of the coating film after deterioration (for example, discoloration of the wet-dry alternating portion of the coating film due to use). ..

According to the present invention, even if the amount of organic antifouling agent is reduced, antifouling property is exhibited for a long period of time, and excellent physical properties such as suppression of crack generation for a long period of time are maintained, and the drying property and coating film are maintained. It is an object of the present invention to provide an environmental load-reducing antifouling coating composition which is excellent in aesthetics by forming an antifouling coating film having excellent strength and further suppressing discoloration of the coating film after deterioration. A further object of the present invention is to provide an antifouling coating film, a base material with an antifouling coating film, and a method for producing the same, which are formed by the antifouling coating composition.

As a result of diligent studies by the inventors, they have found that the above problems can be solved by using the antifouling coating composition shown below, and have completed the present invention.
The gist of the present invention is as follows.
<1> Anti-protection containing a hydrolyzable polymer (A) containing a metal ester group, zinc oxide (B), a monocarboxylic acid compound (C) and / or a metal ester thereof, and an organic antifouling agent (D). In the antifouling coating composition, the content of zinc oxide (B) in the solid content of the antifouling coating composition is 55% by mass or more and 75% by mass or less, and the content of the antifouling coating composition in the solid content is 55% by mass or more. The content of the monocarboxylic acid compound (C) and / or its metal ester is 0.1% by mass or more and 10% by mass or less, and the content of the organic antifouling agent (D) in the solid content of the antifouling coating composition. An antifouling coating composition having an amount of 10% by mass or less.
<2> The antifouling coating composition according to <1>, wherein the metal ester group contained in the hydrolyzable polymer (A) is represented by the following formula (1).

(In formula (1), M indicates copper or zinc, and * indicates the bonding position.)

<3> The hydrolyzable polymer (A) is represented by the polymer (A1) having a structural unit derived from the polymerizable compound represented by the following formula (1-1) and the following formula (1-2). The antifouling coating composition according to <1> or <2>, which contains at least one selected from the group consisting of a polymer (A2) having a structural unit derived from a polymerizable compound.

(In formula (1-1), R ¹¹ independently represents a monovalent group containing a terminal ethylenically unsaturated group, and M represents copper or zinc.)

(In the formula (1-2), R ²¹ represents a monovalent group containing a terminal ethylenically unsaturated group, and R ²² is a monovalent group having 1 to 30 carbon atoms and not containing a terminal ethylenically unsaturated group. Indicates an organic group, where M indicates copper or zinc.)

<4> The hydrolyzable polymer (A) is a polymer (A1') having a structural unit derived from a polymerizable compound represented by the following formula (1-1') and the following formula (1-2'). The protection according to any one of <1> to <3>, which contains at least one selected from the group consisting of polymers (A2') having a structural unit derived from the polymerizable compound represented by. Dirty paint composition.

(In formula (1-1'), R ¹² independently represents a hydrogen atom or a methyl group, and M represents copper or zinc.)

(In the formula (1-2'), R ²³ represents a hydrogen atom or a methyl group, R ²⁴ represents a monovalent organic group having 1 to 30 carbon atoms and containing no terminal ethylenically unsaturated group, and M represents a monovalent organic group. Indicates copper or zinc.)

<5> The antifouling coating composition according to any one of <1> to <4>, wherein the organic antifouling agent (D) is an organic antifouling agent excluding a pyrithion compound.
<6> The organic antifouling agent (D) is 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, (+/-) -4-. [1- (2,3-Dimethylphenyl) ethyl] -1H-imidazole, and at least one selected from the group consisting of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one. , <5>. The antifouling coating composition.
<7> An antifouling coating film formed from the antifouling coating composition according to any one of <1> to <6>.
<8> A base material with an antifouling coating film coated with the antifouling coating film according to <7>.
<9> The base material with an antifouling coating film according to <8>, wherein the base material is selected from the group consisting of ships, underwater structures, and fishery materials.
<10> The step (I) of applying or impregnating the base material with the antifouling coating composition according to any one of <1> to <6> to obtain a coated body or an impregnated body, and the coated body or impregnation. A method for producing a base material with an antifouling coating, which comprises the step (II) of drying the body.
<11> The step (i) of forming an antifouling coating film obtained by drying the antifouling coating composition according to any one of <1> to <6>, and using the antifouling coating film as a base material. A method for producing a base material with an antifouling coating film, which comprises the step (ii) of sticking.

According to the present invention, even if the amount of organic antifouling agent is reduced, antifouling property is exhibited for a long period of time, and excellent physical properties such as suppression of crack generation for a long period of time are maintained, and dryness and dryness are maintained. An antifouling coating film having excellent coating film strength is formed, and discoloration of the coating film after deterioration is suppressed, so that an environmental load-reducing antifouling coating composition having excellent aesthetics can be provided. Further, according to the present invention, it is possible to provide an antifouling coating film, a base material with an antifouling coating film, and a method for producing the same, which are formed by the antifouling coating composition.

FIG. 1 is a schematic view of a coating film cross section of each evaluation of the damage resistance of the antifouling coating film in the examples.

Hereinafter, the antifouling coating composition, the antifouling coating film, the base material with the antifouling coating film, the method for producing the same, and the antifouling method according to the present invention will be described in detail.
In the following description, "(meth) acrylic acid" and "(meth) acrylate" mean acrylic acid or methacrylic acid, and acrylate or methacrylate, respectively.

[Anti-fouling paint composition]
The antifouling coating composition of the present invention (hereinafter, also simply referred to as “coating composition”) is a hydrolyzable polymer (A) containing a metal ester group (hereinafter, simply “hydrolyzable polymer (A)). (Also referred to as), zinc oxide (B), monocarboxylic acid compound (C) and / or a metal ester thereof (hereinafter, also referred to as “monocarboxylic acid component”), and an organic antifouling agent (D). The content of zinc oxide (B) in the solid content of the antifouling coating composition is 55% by mass or more and 75% by mass or less, and the monocarboxylic acid compound (C) and / / in the solid content of the antifouling coating composition. Alternatively, the content of the metal ester thereof is 0.1% by mass or more and 10% by mass or less, and the content of the organic antifouling agent (D) in the solid content of the antifouling coating composition is 10% by mass or less.
According to the present invention, even if the amount of organic antifouling agent is reduced, antifouling property is exhibited for a long period of time, cracks are suppressed for a long period of time, and excellent physical properties are maintained for a long period of time. And an antifouling coating composition for forming an antifouling coating film having excellent coating film strength can be provided. Further, it is possible to provide an environmental load-reducing antifouling coating composition which suppresses discoloration of the coating film after deterioration and has excellent aesthetics.
Due to the growing interest in environmental problems in recent years, it is desired to reduce the antifouling agent component contained in the antifouling coating composition in order to reduce the environmental load. In particular, since many organic antifouling agents affect the drying property, coating film strength, and coating film physical properties, the amount of the paint added should be the optimum amount in consideration of the affinity with the resin and other components. is necessary. If the amount of organic antifouling agent added is too large or too small, problems will occur.
For example, among organic antifouling agents, tralopyryl may affect the drying property and the strength of the coating film, and if the amount added is too large, the drying property and the strength of the coating film are lowered.
In addition, some organic antifouling agents cause discoloration of the coating film due to the influence of ultraviolet rays, which impairs the aesthetic appearance. For example, pyrithion compounds are particularly prone to discoloration. Reducing the amount of organic antifouling agent as much as possible not only reduces the environmental load as described above, but also improves the economic merit of reducing the amount of expensive organic antifouling agent, and the improvement of various coating film performances such as improvement of coating film physical properties and discoloration resistance. Is also connected.
The good physical properties of the coating film mean that the occurrence of cracks and swelling in the formed dry coating film is suppressed.

According to the present invention, by increasing the amount of zinc oxide and using a specific amount of a monocarboxylic acid component, antifouling properties are exhibited for a long period of time even if the amount of an organic antifouling agent such as a pyrithion compound is significantly reduced. The physical properties of the coating film are maintained for a long period of time, such as excellent crack resistance, excellent drying properties and coating film strength, and discoloration of the coating film after deterioration is suppressed, and environmental load-reducing antifouling with excellent aesthetics. A coating composition could be provided. Further, according to the present invention, there are provided an antifouling coating film formed by the antifouling coating composition, a base material with an antifouling coating film and a method for producing the same, and an antifouling method using the antifouling coating film. be able to.
That is, one of the features of the present invention is to reduce the amount of an organic antifouling agent such as a pyrithion compound. In particular, pyrithion compounds tend to be discolored by ultraviolet rays, and copper pyrithion itself is colored dark green and has high coloring power, so it is disadvantageous for obtaining a highly saturated and vivid color coating film. is there. In recent years, in large passenger ships and the like, it has been desired to obtain a coating film having a bright color and preventing discoloration due to aging deterioration and having a good aesthetic appearance.
On the other hand, when the amount of the pyrithion compound is reduced or the compounding formulation does not contain the pyrithion compound, the initial drying property, the damage resistance, the physical properties of the coating film and the like may be deteriorated.
In the present invention, in an antifouling coating composition containing a hydrolyzable polymer (A) containing a metal ester group, the amount of zinc oxide (B) is increased and a monocarboxylic acid component is used in combination to prevent organic substances. Even if the composition has a low content of the contaminant (D), it is characterized in that it has both high antifouling property and excellent aesthetic appearance. In particular, the antifouling coating composition of the present invention can obtain sufficient antifouling properties even when only the organic antifouling agent (D) excluding the pyrithion compound is used.
Usually, when a large amount of zinc oxide is added as in the present invention, the viscosity increases, the coating workability deteriorates, and coating film defects such as cracks in the coating film occur. The present invention is also characterized by using a monocarboxylic acid component in combination. It was found that the monocarboxylic acid component plays a role as a dispersant, and by adding an optimum amount, the increase in the viscosity of the paint is suppressed even if a large amount of zinc oxide is contained, and the effect of suppressing the occurrence of cracks is simultaneously exhibited.
In particular, when the composition does not contain cuprous oxide, the antifouling property is significantly reduced when the content of the organic antifouling agent such as a pyrithion compound is reduced. Since copper oxide is red to reddish brown, it is disadvantageous for an antifouling coating composition containing copper oxide to obtain a highly saturated and brightly colored coating film. The antifouling coating composition of the present invention is particularly effective for an antifouling coating composition containing no cuprous oxide because excellent antifouling properties can be obtained even when the composition does not contain cuprous oxide. is there.
As described above, there is a high demand for an environment-friendly antifouling paint having high performance and a reduced amount of organic antifouling agent components, and the present invention can solve the above-mentioned problems.

Although the detailed mechanism of action for obtaining the above effects is not always clear, some of them are presumed as follows. That is, by containing the hydrolyzable polymer (A) having a metal ester group, the antifouling coating film is imparted with appropriate water resistance and renewability from the surface in water, and further, a specific amount of zinc oxide is provided. By containing (B), a monocarboxylic acid component and a certain amount of organic antifouling agent (D), it is excellent in drying property, coating film strength, discoloration resistance of the coating film after deterioration, and high antifouling property is maintained. It is probable that the antifouling coating film was obtained.
In the present invention, it is preferable that the antifouling coating film has an appropriate water resistance and an appropriate coating film renewability in water. There is a problem that the antifouling component elutes too quickly due to the decrease in water resistance and long-term antifouling property cannot be obtained. In addition, the decrease in coating film renewability reduces the antifouling property. Problems such as being recognized occur.
Hereinafter, each component contained in the antifouling coating composition of the present invention will be described in detail.

<Hydrolytic polymer (A) containing a metal ester group>
The antifouling coating composition of the present invention contains a hydrolyzable polymer (A) containing a metal ester group (hydrolyzable polymer (A)).
Here, the "metal ester group" is a salt formed by a metal and an organic acid, and is preferably a group formed by bonding a metal and a carboxylic acid. Further, the "polyvalent metal ester group" or "divalent metal ester group" described later refers to a group formed by bonding a polyvalent metal or a divalent metal with an organic acid.
As the metal ester group, a polyvalent metal ester group is preferable, and a divalent metal ester group represented by the following formula (1) is more preferable.

(In equation (1), M indicates a metal and * indicates a bonding position.)

Examples of the metal constituting the metal ester group include magnesium, calcium, neodymium, titanium, zirconium, iron, ruthenium, cobalt, nickel, copper, zinc, and aluminum.
In the formula (1), M is a divalent metal, and a divalent metal can be appropriately selected and used from the above-mentioned metals. Among these, Group 10 to 12 metals such as nickel, copper, and zinc are preferable, copper and zinc are more preferable, and zinc is even more preferable.
* In the formula (1) represents a bond position and indicates that it is linked to an arbitrary group, preferably an arbitrary organic group.

The hydrolyzable polymer (A) may have a group represented by the above formula (1) at the end of the main chain or the side chain, and the main chains are represented by the formula (1). It may be crosslinked by a divalent group including the group to be subjected to. Further, the hydrolyzable polymer (A) may be an addition polymerization type polymer obtained by polymerizing an ethylenically unsaturated compound, and like polyester or polyamide, polycondensation obtained by polycondensation. It may be a type polymer, and is not particularly limited. Among these, an addition polymerization type polymer obtained by polymerization of an ethylenically unsaturated compound is preferable.

The hydrolyzable polymer (A) is a polymer (A1) having a structural unit derived from a polymerizable compound represented by the following formula (1-1) and a polymerizable polymer represented by the following formula (1-2). It preferably contains at least one selected from the group consisting of polymers (A2) having a structural unit derived from the compound. The hydrolyzable polymer (A) is derived from a structural unit derived from a polymerizable compound represented by the following formula (1-1) and a polymerizable compound represented by the following formula (1-2). It may have both constituent units, in which case it is a polymer (A1). That is, the polymer (A1) is a polymer having at least a structural unit derived from a polymerizable compound represented by the following formula (1-1), and the polymer (A2) is a polymer having the following formula (1-2). It has a structural unit derived from the polymerizable compound represented by, and does not have a structural unit derived from the polymerizable compound represented by the following formula (1-1).

When the hydrolyzable polymer (A) is a polymer (A1) having a structural unit derived from a polymerizable compound represented by the following formula (1-1), it is represented by the following formula (1-1). A polymerizable compound may be obtained by using a polymerizable compound as a monomer component, or a polymer having a carboxy group may be obtained and then metal esterified to form a crosslinked structure to obtain a polymer (A1). The polymer (A1) is preferably obtained by using the polymerizable compound represented by the formula (1-1) as a monomer component from the viewpoint of ease of production, although the present invention is not particularly limited.
Similarly, the polymer (A2) having a structural unit derived from the polymerizable compound represented by the following formula (1-2) is a monomer component of the polymerizable compound represented by the following formula (1-2). It may be obtained by using as a polymer, or by metal esterifying after obtaining a polymer having a carboxy group, and the present invention is not particularly limited, but from the viewpoint of ease of production, the following formula (1- It is preferable to obtain the polymer (A2) by using the polymerizable compound represented by 2) as a monomer component.
In the following description, the polymerizable compound represented by the following formula (1-1) is a monomer (a1-1), and the polymerizable monomer represented by the following formula (1-2) is a monomer ( Also called a1-2). Further, the monomer (a1-1) and the monomer (a1-2) are generically also referred to as a monomer (a1).

(In formula (1-1), R ¹¹ independently represents a monovalent group containing a terminal ethylenically unsaturated group, and M represents copper or zinc.)

In the formula (1-1), R ¹¹ represents a monovalent group containing a terminal ethylenically unsaturated group (CH ₂ = C <), and the carbon number of R ¹¹ is preferably 2 or more and 50 or less. It is preferably 2 or more and 30 or less, more preferably 2 or more and 10 or less, and even more preferably 2 or more and 6 or less. R ¹¹ may have an ethylenically unsaturated group at the terminal and may have an ethylenically unsaturated group other than the terminal, but it is more preferable to have an ethylenically unsaturated group only at the terminal.
R ¹¹ is preferably an unsaturated aliphatic group containing a terminal ethylenically unsaturated group, and the unsaturated aliphatic group has an ester bond, an amide bond, and an ether bond in the carbon chain. May be good. Specific examples R ^11, acrylic acid (2-propenoic acid), methacrylic acid (2-methyl-2-propenoic acid), 3-butenoic acid, 4-pentenoic acid, 10-undecenoic acid, 3- (meth) Examples thereof include groups obtained by removing a carboxy group from an aliphatic unsaturated monocarboxylic acid such as acrylicoyloxypropionic acid and 3- (meth) acryloyloxy-2-methylpropionic acid. Further, a group obtained by removing one carboxy group from an aliphatic unsaturated dicarboxylic acid containing a terminal ethylenically unsaturated group such as itaconic acid is exemplified.
Among these, R ¹¹ is preferably a group obtained by removing a carboxy group from an aliphatic unsaturated monocarboxylic acid containing a terminal ethylenically unsaturated group, and is preferably acrylic acid, methacrylic acid, or (meth) acryloyloxyalkyl. A group obtained by removing a carboxy group from a carboxylic acid is more preferable, and a group obtained by removing a carboxy group from an acrylic acid or a methacrylate is further preferable.

Examples of the polymerizable compound represented by the formula (1-1) (monomer (a1-1)) include zinc diacrylate, zinc dimethacrylate, zinc acrylic acid (methacrylic acid), and di (3-acryloyloxypropion). Acid) Zinc, di (3-methacryloyloxypropionic acid) zinc, di (3- (meth) acryloyloxy-2-methylpropionic acid) zinc, copper diacrylate, copper dimethacrylate, copper acrylic acid (methacrylic acid), Examples thereof include di (3-acryloyloxypropionic acid) copper, di (3-methacryloyloxypropionic acid) copper, and di (3- (meth) acryloyloxy-2-methylpropionic acid) copper.

(In the formula (1-2), R ²¹ represents a monovalent group containing a terminal ethylenically unsaturated group, and R ²² is a monovalent group having 1 to 30 carbon atoms and not containing a terminal ethylenically unsaturated group. Indicates an organic group, where M indicates copper or zinc.)

In formula (1-2), R ²¹ represents a monovalent group containing a terminal ethylenically unsaturated group. As R ²¹ , the same group as R ¹¹ in the formula (1-1) is exemplified, and the preferred embodiment is also the same.
In the formula (1-2), R ²² represents a monovalent organic group having 1 to 30 carbon atoms and containing no terminal ethylenically unsaturated group. Examples of R ²² include an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, and an aroma having 6 to 30 carbon atoms, which do not contain a terminal ethylenically unsaturated group. Group hydrocarbon groups are exemplified. These groups may have substituents. A hydroxyl group is exemplified as the substituent.
The aliphatic hydrocarbon group may be linear or branched, and may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. When R ²² is an unsaturated aliphatic hydrocarbon group, R ²² does not contain a terminal ethylenically unsaturated group. The number of carbon atoms of the aliphatic hydrocarbon group is 1 or more and 30 or less, preferably 1 or more and 28 or less, more preferably 1 or more and 26 or less, and further preferably 1 or more and 24 or less carbon atoms. The aliphatic hydrocarbon group may be further substituted with an alicyclic hydrocarbon group or an aromatic hydrocarbon group.
The alicyclic hydrocarbon group may be a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group. The number of carbon atoms of the alicyclic hydrocarbon group is 3 or more and 30 or less, preferably 4 or more and 20 or less, more preferably 5 or more and 16 or less, and further preferably 6 or more and 12 or less. The alicyclic hydrocarbon group may be further substituted with an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The aromatic hydrocarbon group has 6 or more and 30 or less carbon atoms, preferably 6 or more and 24 or less carbon atoms, more preferably 6 or more and 18 or less carbon atoms, and further preferably 6 or more and 10 or less carbon atoms. The aromatic hydrocarbon group may be further substituted with an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.
In addition, R ²² has 1 or more and 30 or less carbon atoms as a whole.

R ²² is preferably an organic acid residue formed from a monobasic acid, specifically, versatic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, Examples are groups of organic acids selected from the group consisting of neo-abietic acid, pimalic acid, dehydro-abietic acid, 12-hydroxystearic acid, and naphthenic acid minus the carboxy group.
Among these, a group obtained by removing a carboxy group from abietic acid, versatic acid and naphthenic acid is preferable, and a group obtained by removing a carboxy group from abietic acid and versatic acid is more preferable.

The polymer (A2) having a structural unit derived from the polymerizable compound represented by the formula (1-2) is a polymerizable compound represented by the formula (1-2) (monomer (a1-2)). It is preferable that the structural unit is obtained by polymerizing only the terminal ethylenically unsaturated group inside. Examples of the monomer (a1-2) include 3- (meth) acryloyloxypropionic acid (avietate) zinc, 3- (meth) acryloyloxypropionic acid (versatic acid) zinc, and (meth) acrylic acid (avietic acid). Zinc, (meth) acrylic acid (versatic acid) zinc, (meth) acrylic acid (naphthenic acid) zinc, 3- (meth) acryloyloxypropionic acid (avietic acid) copper, 3- (meth) acryloyloxypropionic acid (versatic) A polymerizable compound selected from the group consisting of (acid) copper, (meth) acrylic acid (avietic acid) copper, (meth) acrylic acid (versatic acid) copper, and (meth) acrylic acid (naphthenic acid) copper is exemplified. Acrylic acid.

In the formulas (1-1) and (1-2), M represents copper or zinc, and zinc is preferable.

The hydrolyzable polymer (A) is represented by a polymer (A1') having a structural unit derived from a polymerizable compound represented by the following formula (1-1') and a following formula (1-2'). It is more preferable to contain at least one selected from the group consisting of polymers (A2') having a structural unit derived from the polymerizable compound. The polymer (A1) is preferably a polymer (A1'), and the polymer (A2) is preferably a polymer (A2'). Further, the hydrolyzable polymer (A) is divided into a structural unit derived from a polymerizable compound represented by the following formula (1-1') and a polymerizable compound represented by the following formula (1-2'). It may have both with the building block from which it is derived.

(In formula (1-1'), R ¹² independently represents a hydrogen atom or a methyl group, and M represents copper or zinc.)

Examples of the polymerizable compound represented by the formula (1-1') include zinc diacrylate, zinc dimethacrylate, zinc acrylic acid (methacrylic acid), copper diacrylate, copper dimethacrylate, and copper acrylate (methacrylic acid). Is exemplified.

(In the formula (1-2'), R ²³ represents a hydrogen atom or a methyl group, R ²⁴ represents a monovalent organic group having 1 to 30 carbon atoms and containing no terminal ethylenically unsaturated group, and M represents a monovalent organic group. Indicates copper or zinc.)

In the formula (1-2'), as R ²⁴ , the same group as R ²² in the above formula (1-2) is exemplified, and the preferred embodiment is also the same.
Examples of the polymerizable compound represented by the above formula (1-2') include (meth) acrylic acid (avietate) zinc, (meth) acrylic acid (versatic acid) zinc, and (meth) acrylic acid (naphthenic acid) zinc. , (Meta) acrylic acid (avietic acid) copper, (meth) acrylic acid (versatic acid) copper, and (meth) acrylic acid (naphthenic acid) copper are exemplified.

In the formula (1-1') and the formula (1-2'), M represents copper or zinc, and is preferably zinc.

The polymerizable compound represented by the formula (1-1), the polymerizable compound represented by the formula (1-1'), and the polymerization represented by the formula (1-2) in the hydrolyzable polymer (A). The total content of the constituent units derived from the sex compound and the polymerizable compound represented by the formula (1-2'), that is, the total content of the constituent units derived from the monomer (a1) is the total constituent units. Among them, preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 40% by mass or less, further preferably 10% by mass or more and 35% by mass or less, still more preferably 15% by mass or more and 32% by mass or less. is there.
The ratio of each content (mass) of the constituent units derived from each monomer in the hydrolyzable polymer (A) is the ratio of the charged amount (mass) of each of the monomers used in the polymerization reaction. Can be considered the same.

The hydrolyzable polymer (A) preferably has a structural unit based on another monomer (a2) in addition to the structural unit having a metal ester group.
The other monomer (a2) is preferably a monomer having an ethylenically unsaturated group, and specifically, methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth). Acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n- Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate , Alkyl (meth) acrylates such as phenyl (meth) acrylates, benzyl (meth) acrylates or aryl (meth) acrylates;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 3-methoxy-n-propyl (meth) acrylate, 2- Propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, isobutoxybutyl diglycol (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate , Butoxypolyethylene glycol (meth) acrylate, alkoxyalkyl (meth) acrylate such as phenoxypolyethylene glycol (meth) acrylate, alkoxypolyalkylene glycol (meth) acrylate, aryloxyalkyl (meth) acrylate, or arylpolyalkylene glycol (meth). Acrylate;
Hydroxy such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. Alkyl (meth) acrylate or hydroxyaryloxyalkyl (meth) acrylate;
Glycidyl (meth) acrylate;
Organosiloxane group-containing (meth) acrylate;
Examples thereof include vinyl compounds such as styrene, α-methylstyrene, vinyl acetate, vinyl benzoate, vinyltoluene, acrylonitrile, vinylpyridine, vinylpyrrolidone and vinyl chloride. These monomers may be used alone or in combination of two or more.

Among these, alkyl (meth) acrylate (the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, still more preferably 1 or more and 6 or less, still more preferably 1 or more and 4 or less), alkoxy. Alkyl (meth) acrylate (the alkyl group in the alkoxy group and the number of carbon atoms of the alkyl group are preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, still more preferably 1 or more and 6 or less, still more preferably 1. (4 or less), hydroxyalkyl (meth) acrylate (the number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, still more preferably 1 or more and 6 or less, still more preferably 1 or more and 4 or less). Is preferable.
From the viewpoint of good coating film physical properties and long-term antifouling property, it is preferable to contain at least an alkyl (meth) acrylate as the monomer (a2), and the alkyl (meth) acrylate in the monomer (a2). The content is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more.
The content of the structural unit derived from the monomer (a2) in the hydrolyzable polymer (A) shall be 40% by mass or more and 99% by mass or less in all the structural units from the viewpoint of long-term antifouling property. Is more preferable, 60% by mass or more and 95% by mass or less is more preferable, 65% by mass or more and 90% by mass or less is further preferable, and 68% by mass or more and 85% by mass or less is further preferable.

The hydrolyzable polymer (A) can be produced, for example, by the following procedure.
The monomer (a1) is, for example, a metal compound (preferably an inorganic metal compound, specifically, an oxide of copper or zinc, a hydroxide, a chloride, an organic acid salt (for example, zinc acetate, etc.), etc.). And an organic acid such as methacrylic acid or acrylic acid or an esterified product thereof can be synthesized by a known method such as heating and stirring in the presence of an organic solvent and water at a temperature lower than the decomposition temperature of the metal salt.
More specifically, first, a mixed solution of a solvent and a metal component such as zinc oxide is stirred while being heated to about 50 ° C. or higher and 80 ° C. or lower, and an organic acid such as methacrylic acid or acrylic acid is added to the mixture. Alternatively, a monomer (a1) having a metal ester group is prepared by dropping a mixed solution of an ester thereof and water or the like and further stirring the mixture.
Next, a solvent is placed in a newly prepared reaction vessel and heated to about 80 ° C. or higher and 120 ° C. or lower, and the monomer (a1) having the metal ester group, the other monomer (a2), and polymerization are added thereto. A hydrolyzable polymer (A) having a metal ester group can be obtained by dropping a mixed solution of an initiator, a chain transfer agent, a solvent and the like and carrying out a polymerization reaction.
The ratio of each content (mass) of the structural unit derived from each monomer in the hydrolyzable polymer (A) is the ratio of the charged amount (mass) of each of the monomers used in the polymerization reaction. Can be considered the same.

The polymerization initiator that can be used in the production of the hydrolyzable polymer (A) is not particularly limited, and various radical polymerization initiators can be used. Specifically, benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, sodium persulfate, 2,2'-azobisisobutyronitrile [AIBN], 2,2'. -Azobis (2-methylbutyronitrile) [AMBN], 2,2'-azobis (2,4-dimethylvaleronitrile) [ADVN], tert-butyl peroxide [TBPO] and the like can be mentioned. These polymerization initiators may be used alone or in combination of two or more. These radical polymerization initiators may be added into the reaction system only at the start of the reaction, or may be added into the reaction system both at the start of the reaction and during the reaction.
The amount of the polymerization initiator used in the production of the hydrolyzable polymer (A) is preferably 2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass in total of each of the monomers.

The chain transfer agent that can be used in the production of the hydrolyzable polymer (A) is not particularly limited, and for example, α-methylstyrene dimer, thioglycolic acid, diterpene, tarpinolene, γ-terpinen; tert-dodecyl mercaptan. , And mercaptans such as n-dodecyl mercaptan; halides such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane; secondary alcohols such as isopropanol; glycerin and the like. These chain transfer agents may be used alone or in combination of two or more.
When a chain transfer agent is used in the production of the hydrolyzable polymer (A), the amount used is preferably 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass in total of each of the monomers. is there.

Examples of the solvent that can be used for producing the hydrolyzable polymer (A) include aromatic solvents such as toluene, xylene, and mesitylen; propanol, butanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and the like. Alcohols; ketones such as methyl ethyl ketone, methyl isobutyl ketone and methyl amyl ketone; esters such as ethyl acetate and butyl acetate; water and the like. These solvents may be used alone or in combination of two or more.
When a solvent is used in the production of the hydrolyzable polymer (A), the amount used is not particularly limited, but is preferably 5 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass in total of each of the monomers. Is.

The method for producing the hydrolyzable polymer (A) is not limited to this, and the polymer (a3) having a carboxy group, the monocarboxylic acid compound (C) described later, and a metal compound (preferably). The carboxy group of the polymer (a3) by reacting with an inorganic metal compound, specifically, an oxide of copper or zinc, a hydroxide, a chloride, an organic acid salt (for example, zinc acetate, etc.), etc. It may be produced by a method of introducing a metal ester group into the polymer or a method of reacting a polymer (a3) having a carboxy group with a metal compound to introduce a metal ester bridge into the polymer.

Examples of the polymer (a3) having a carboxy group include a polyester-based polymer (a3-1) and an acrylic-based polymer (a3-2), and a polyester-based polymer (a3-1) is preferable.
Examples of the polyester-based polymer (a3-1) include polyester resins having an acid group.
The solid acid value of the polyester polymer (a3-1) is preferably 30 mgKOH / g or more and 250 mgKOH / g or less, and more preferably 50 mgKOH / g or more and 200 mgKOH / g or less.
The polyester polymer (a3-1) is obtained by reacting one or more polyhydric alcohols with one or more polyvalent carboxylic acids and / or anhydrides thereof, and any kind can be used in any amount. The acid value and viscosity can be adjusted by the combination.
Examples of the polyester polymer (a3-1) include trivalent or higher valent alcohols (a3-11), dibasic acids and / or anhydrides thereof (a3-) as described in International Publication No. 2014/010702. 12) and a divalent alcohol (a3-13) are reacted, and then an alicyclic dibasic acid and / or an anhydride thereof (a3-14) is further reacted to obtain a preferred example. To.

As described above, a method of reacting the polyester-based polymer (a3-1) with the monocarboxylic acid compound (C) and the metal compound, or reacting the polyester-based polymer (a3-1) with the metal compound. The hydrolyzable polymer (A) can also be produced by the method of causing.
As the monocarboxylic acid compound (C) to be reacted with such a polyester-based polymer (a3-1), those described later can be used, and among them, rosins are preferably used, and the metal compound is preferably. For example, metal oxides such as zinc oxide and copper oxide can be used, and zinc oxide is particularly preferable.

As the acrylic polymer (a3-2), acrylic acid, methacrylic acid, 3- (meth) acryloyloxypropionic acid, 3- (meth) acryloyloxy-2-methylpropion as a polymerizable compound (monomer). Examples thereof include an acrylic polymer (a3-2) containing an unsaturated carboxylic acid such as an acid and a carboxy group obtained by radical polymerization using another monomer (a2) if necessary.
Similar to the polyester polymer (a3-1), the acrylic polymer (a3-2), the monocarboxylic acid compound (C), and the metal compound (preferably an inorganic metal compound, specifically copper or By a method of reacting with a zinc oxide, a hydroxide, a chloride, an organic acid salt (for example, zinc acetate, etc.), or a method of reacting the acrylic polymer (a3-2) with a metal compound. , The hydrolyzable polymer (A) can also be prepared.

The content of copper and / or zinc in the hydrolyzable polymer (A) is determined in the hydrolyzable polymer (A) from the viewpoint of forming an antifouling coating film having excellent coating renewability and antifouling property. It is preferably 0.5% by mass or more and 25% by mass or less, more preferably 1% by mass or more and 20% by mass or less, and further preferably 3% by mass or more and 15% by mass or less. The content of copper and / or zinc can be measured by an X-ray diffractometer or an ICP emission spectrometer, and is appropriately adjusted by blending the monomer used when synthesizing the hydrolyzable polymer (A). be able to.

The acid value of the hydrolyzable polymer (A) is preferably 30 mgKOH / g or more and 250 mgKOH / g or less from the viewpoint of setting the dissolution rate of the obtained antifouling coating film in water within a desired range.
When the acid value is 30 mgKOH / g or more, the metal content in the hydrolyzable polymer (A) is appropriate, and an antifouling coating film having excellent antifouling properties can be obtained, which is preferable. Further, when the acid value is 250 mgKOH / g or less, an antifouling coating film having excellent long-term antifouling property can be obtained, which is preferable.

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the hydrolyzable polymer (A) are the viscosity and storage stability of the antifouling coating composition, the elution rate (renewability) of the obtained antifouling coating film, and the like. It is preferable to make appropriate adjustments in consideration of.
The number average molecular weight (Mn) of the hydrolyzable polymer (A) is preferably 500 or more and 30,000 or less, and more preferably 800 or more and 10,000 or less. The weight average molecular weight (Mw) of the hydrolyzable polymer (A) is preferably 1,000 or more and 200,000 or less, and more preferably 1,200 or more and 20,000 or less.
The number average molecular weight (Mn) and the weight average molecular weight (Mw) are determined by measuring by gel permeationography and converting with standard polystyrene.

The hydrolyzable polymer (A) may be used alone or in combination of two or more.
The content of the hydrolyzable polymer (A) in the antifouling coating composition is determined from the viewpoint of obtaining an antifouling coating film having excellent coating workability, surface renewal durability and water resistance of the antifouling coating composition in the present invention. In the solid content of the antifouling coating composition, preferably 1% by mass or more and 44.9% by mass or less, more preferably 5% by mass or more and 35% by mass or less, still more preferably 10% by mass or more and 30% by mass or less, further. It is preferably 15% by mass or more and 25% by mass or less.
In the present invention, when two or more kinds of the hydrolyzable polymer (A) are contained, the above content is a preferable range as the total content of the hydrolyzable polymer (A), and each component described later. The same applies to.
The solid content of the antifouling coating composition refers to the residual heating residue when the antifouling coating composition is dried in a hot air dryer at 108 ° C. for 3 hours to volatilize a solvent or the like.

<Zinc oxide (B)>
The antifouling coating composition of the present invention contains zinc oxide (B). By using a specific amount of zinc oxide (B) together with the hydrolyzable polymer (A), an antifouling coating film capable of maintaining high antifouling property can be obtained.
The effect is not a mere combination of the hydrolyzable polymer (A), zinc oxide (B) and the effects of each, but a synergistic effect that occurs only when these are used in combination.

The content of zinc oxide (B) in the antifouling coating composition of the present invention maintains good antifouling properties for a long period of time, and an antifouling coating film having good coating material properties can be obtained. From the point of view, the solid content of the antifouling coating composition of the present invention is 55% by mass or more and 75% by mass or less, preferably 60% by mass or more and 72% by mass or less, and more preferably 63% by mass or more and 70% by mass or less.
When zinc oxide (B) is not more than the above regulation, sufficient antifouling property is obtained when the content of the organic antifouling agent (D) in the solid content of the antifouling coating composition is 10% by mass or less. If it is more than the above specified value, coating film defects such as cracks occur, and sufficient coating film physical properties cannot be obtained.
Further, in the present invention, by setting the content of zinc oxide (B) within the above range, the content of the hydrolyzable polymer (A) can be suppressed as a result, and the antifouling coating composition can be inexpensive. It is also preferable in that it can be prepared in.
The average particle size of zinc oxide (B) is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less. The average particle size of zinc oxide (B) is the median diameter (D ₅₀ ) in the particle size distribution and can be measured by the laser diffraction / scattering method. Further, for the product, the published value may be adopted.

<Monocarboxylic acid compound (C) and / or its metal ester>
The antifouling coating composition of the present invention contains a monocarboxylic acid compound (C) and / or a metal ester thereof (monocarboxylic acid component).
In the present invention, the monocarboxylic acid component improves the renewability of the formed antifouling coating film from the surface in water, and when the antifouling coating film contains an antifouling agent, promotes its release into water. It promotes the improvement of antifouling property and further imparts appropriate water resistance to the antifouling coating film.
Examples of the monocarboxylic acid compound (C) include rosins such as gum rosin, wood rosin and tall oil rosin, rosin derivatives such as hydrogenated rosin and disproportionate rosin, and examples of other monocarboxylic acid compounds are aliphatic or aliphatic. An alicyclic monocarboxylic acid and the like can be mentioned. Specific examples of other monocarboxylic acid compounds include trimethylisobutenylcyclohexenecarboxylic acid, naphthenic acid, versatic acid, stearic acid, salicylic acid and the like. These may be used alone or in combination of two or more. It is more preferable that the monocarboxylic acid compound (C) is a rosin such as gum rosin, wood rosin or tall oil rosin, or a rosin derivative such as hydrogenated rosin or disproportionated rosin from the viewpoint of dryness and coating strength.
The monocarboxylic acid compound (C) may form a metal ester, and zinc ester and copper ester are exemplified. The metal ester may be formed in advance before the preparation of the antifouling coating composition, or may be formed by reaction with other coating components during the preparation of the antifouling coating composition.
The metal ester of the monocarboxylic acid compound (C) may correspond to the hydrolyzable polymer (A). In such a case, it is assumed to be the hydrolyzable polymer (A).

The monocarboxylic acid component not only improves the antifouling property but also acts as a pigment dispersant, has a high dispersion effect of metal compounds such as zinc oxide, suppresses an increase in paint viscosity, improves painting workability, and cracks in the coating film. Has a suppressive effect. If the content of the monocarboxylic acid component is small, the effect of suppressing the increase in paint viscosity, improving the coating workability, and suppressing the coating film crack is lost. On the other hand, if the content is too large, the discoloration resistance is lowered and the water resistance is lowered. Problems such as cracks due to this, excessive coating film wearability, thickening of the required film thickness, and inferior long-term antifouling property occur.
The content of the monocarboxylic acid component in the solid content of the antifouling coating composition of the present invention is 0.1% by mass or more and 10% by mass or less, preferably 1.0% by mass or more and 8% by mass or less, more preferably. Is 2% by mass or more and 7% by mass or less, more preferably 2.5% by mass or more and 6% by mass or less.

<Organic antifouling agent (D)>
In order to further improve the antifouling property of the antifouling coating film formed from the antifouling coating composition of the present invention, it is preferable that the antifouling coating composition of the present invention further contains the organic antifouling agent (D). ..
The organic antifouling agent (D) is preferably an organic antifouling agent excluding the pyrithion compound from the viewpoint of suppressing discoloration of the antifouling coating film and suppressing the amount of the organic antifouling agent used. It is preferable that the fouling agent (D) contains substantially no pyrithion compound.
In the present invention, "substantially free of the pyrithion compound" means that the concentration of the pyrithion compound in the solid content of the coating composition is less than 0.1% by mass, preferably 0.05% by mass or less. , More preferably 0.03% by mass or less, still more preferably 0.01% by mass or less.
Here, examples of the pyrithion compound include copper pyrithione, zinc pyrithione, and sodium pyrithione.

Examples of the organic antifouling agent (D) include (+/-)-4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole (also known as medetomidin) and 4,5-dichloro-2. -N-octyl-4-isothiazolin-3-one (also known as DCOIT), 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (also known as traropyryl) ), Pyridintriphenylboran, 4-isopropylpyridinediphenylmethylboran, N, N-dimethyl-N'-(3,4-dichlorophenyl) urea (also known as diuron), N- (2,4,6-trichlorophenyl) Maleimide, 2,4,5,6-tetrachloroisophthalnitrile, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine (also known as cibutrin), bisdimethyldithiocarbamoylzinc Ethylenebisdithiocarbamate (also known as polycarbamate), chloromethyl-n-octyldisulfide, N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide (also known as diclofluanide), tetraalkylti Laum disulfide (also known as TMTD), zinc dimethyldithiocarbamate (also known as dilam), zincethylenebisdithiocarbamate (also known as dineb), 2,3-dichloro-N- (2', 6'-diethylphenyl) maleimide, 2 , 3-Dichloro-N- (2'-ethyl-6'-methylphenyl) maleimide and the like. The organic antifouling agent (D) may be used alone or in combination of two or more.

The (+/-)-4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole is represented by the following formula (2).

The (+/-)-4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole has optical isomers, but only one of the optical isomers is a mixture in any ratio. It may be. Further, an adduct to an imidazolium salt, a metal or the like may be used as a part or all of (+/-)-4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole. Alternatively, an adduct to a metal or the like or an imidazolium salt may be formed in the antifouling coating composition or antifouling coating film of the present invention.

Among these, the organic antifouling agent (D) is 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (also known as traropyryl), (+/ -) -4- [1- (2,3-Dimethylphenyl) ethyl] -1H-imidazole (also known as medetomidine) and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (also known as medetomidin). : DCOIT) is more preferably at least one selected from the group consisting of (+/-)-4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole (also known as medetomidin). And at least one selected from the group consisting of 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (also known as traropyryl) is more preferred. ..

In the antifouling coating composition of the present invention, the content of the organic antifouling agent (D) is determined from the viewpoint of improving the long-term antifouling property of the antifouling coating film to be formed, the balance of the physical properties of the coating film, and the discoloration resistance. The solid content of the antifouling coating composition of the present invention is 10% by mass or less, preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 8% by mass or less, still more preferably. It is 0.1% by mass or more and 6% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less.
The antifouling coating composition of the present invention contains a large amount of zinc oxide (B) and is used in combination with a hydrolyzable polymer (A) and a specific amount of a monocarboxylic acid component to provide an organic antifouling agent (an organic antifouling agent (). Even if the composition contains a small amount of D), it exhibits excellent antifouling properties.

The antifouling coating composition of the present invention may contain an inorganic copper compound as an antifouling agent in addition to the organic antifouling agent (D), but the content thereof is determined by the solid content of the antifouling coating composition. It is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, still more preferably 0.1% by mass or less. It is particularly preferable that the antifouling coating composition of the present invention is substantially free of inorganic copper compounds.
Examples of the inorganic copper compound include cuprous oxide, metallic copper, and rodane copper.
When the antifouling coating composition contains these inorganic copper compounds, the coating film itself tends to be colored by the color of the inorganic copper compound, and from the viewpoint of the degree of freedom in selecting the color of the coating film, the inorganic copper compound The content is preferably low.

<Other optional ingredients>
In addition to the above-mentioned components, the antifouling coating composition of the present invention contains an extender pigment (E), a coloring pigment (F), a plasticizer (G), a pigment dispersant (H), and a sagging inhibitor (I), if necessary. ), Anti-sedimentant (J), dehydrating agent (K), solvent (L), other resin (M) and the like may be contained.
The following other optional components will be described.

[Constituent pigment (E)]
The antifouling coating composition of the present invention may contain an extender pigment (E) for the purpose of improving the physical properties of the coating film such as water resistance and crack resistance of the obtained antifouling coating film.
Examples of the extender pigment (E) include talc, silica, mica, clay, potash talc, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate and the like. Among these, talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, and potassium feldspar are preferable. Calcium carbonate and white carbon are also used as a settling inhibitor (J) and a matting agent, which will be described later, respectively. The extender pigment (E) may be used alone or in combination of two or more.

When the extender pigment (E) is contained in the antifouling coating composition of the present invention, the content of the extender pigment (E) is the water resistance, mechanical properties, and antifouling property of the antifouling coating film to be formed. From the viewpoint of improving the above, the antifouling coating composition of the present invention preferably has a solid content of 0.1% by mass or more and 40% by mass or less, more preferably 0.3% by mass or more and 20% by mass or less, and further preferably 0. It is 5.5% by mass or more and 10% by mass or less.

[Coloring pigment (F)]
From the viewpoint of adjusting the color tone of the antifouling coating film formed from the antifouling coating composition of the present invention and imparting an arbitrary color tone, the antifouling coating composition of the present invention contains a coloring pigment (F). May be good.
Examples of the coloring pigment (F) include known organic or inorganic coloring pigments. Examples of the organic coloring pigment include naphthol red and phthalocyanine blue. Examples of the inorganic coloring pigment include carbon black, red iron oxide, barite powder, titanium white, and yellow iron oxide. The coloring pigment (F) may be used alone or in combination of two or more.
Further, in the antifouling coating composition of the present invention, a colorant other than the color pigment (F) such as a dye may be contained together with the color pigment (F) or instead of the color pigment (F).

In the antifouling coating composition of the present invention, the content of the coloring pigment (F) is the coloring property, hiding property, exposure discoloration property, antifouling property, and water coating resistance (mechanical properties) of the obtained antifouling coating film. From the viewpoint of improving the above, the antifouling coating composition of the present invention preferably has a solid content of 0.1% by mass or more and 30% by mass or less, more preferably 0.3% by mass or more and 20% by mass or less, and further preferably 1. It is 0.0% by mass or more and 10% by mass or less.

[Plasticizer (G)]
The antifouling coating composition of the present invention may contain a plasticizer (G) for the purpose of imparting plasticity to the antifouling coating film.
Examples of the plasticizer (G) include tricresyl phosphate (TCP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP) and the like. These plasticizers may be used alone or in combination of two or more.
When the antifouling coating composition of the present invention contains a plasticizer (G), the content thereof is preferably 0.1% by mass or more and 10% by mass or less, preferably 0.5% by mass or less, based on the solid content of the coating composition. It is more preferably mass% or more and 5 mass% or less. When the content of the plasticizer (G) is within the above range, the plasticity of the antifouling coating film can be kept good.

[Pigment Dispersant (H)]
When the antifouling coating composition of the present invention contains an extender pigment (E) or a coloring pigment (F), the antifouling coating composition of the present invention contains a pigment dispersant (H) for the purpose of improving pigment dispersibility. It may be contained.
Examples of the pigment dispersant (H) include known organic or inorganic pigment dispersants. Examples of the pigment dispersant include aliphatic amines or organic acids (for example, "Duomin TDO" (manufactured by LION Corporation), "Disperbyk101" (manufactured by BYK Co., Ltd.)). The pigment dispersant (H) may be used alone or in combination of two or more.

In the antifouling coating composition of the present invention, the content of the pigment dispersant (H) is determined from the viewpoint of improving the effect of reducing the coating viscosity of the antifouling coating composition and the effect of preventing color coding of the antifouling coating. The solid content of the antifouling coating composition of the present invention is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.01% by mass or more and 5% by mass or less.

[Sauce stop agent (I)]
When the base material is coated with the antifouling coating composition of the present invention, the sagging inhibitor (I) (also referred to as a flow inhibitor) is contained from the viewpoint of reducing the occurrence of sagging due to the coating composition. May be good.
Examples of the sagging preventive agent (I) include amide wax, hydrogenated castor oil wax, a mixture thereof, and synthetic fine powder silica. The anti-sauce agent (I) may be used alone or in combination of two or more. As the amide wax, fatty acid amide is preferable.
Among these, the sagging preventive agent (I) is preferably amid wax or synthetic fine silica. When amido wax or synthetic fine powder silica is used as the anti-sagging agent (I), the storage stability of the antifouling coating composition is improved, and after the antifouling coating film is formed, the same type of coating material is applied on the antifouling coating film. When a coating film (topcoat coating film) composed of a composition (antifouling coating composition) or a different coating composition is formed, the adhesion between the antifouling coating film and the topcoat coating film (interlayer adhesion, recoating). It becomes possible to prevent a decrease in sex).
Examples of commercially available products of the anti-sauce agent (I) include "Disparon A630-20X" (manufactured by Kusumoto Kasei Co., Ltd.) and "ASAT-250F" (manufactured by Ito Essential Oil Co., Ltd.).
In the antifouling coating composition of the present invention, the content of the anti-sagging agent (I) is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1 in the solid content of the antifouling coating composition. It is mass% or more and 5 mass% or less.

[Sedimentation inhibitor (J)]
The antifouling coating composition of the present invention may contain a settling inhibitor (J) from the viewpoint of preventing the generation of precipitates during storage and improving the agitation property.
Examples of the sedimentation inhibitor (J) include stearate of Al, Ca, or Zn, polyethylene wax, polyethylene oxide wax, and the like. The sedimentation inhibitor (J) can be used alone or in combination of two or more.
Above all, the sedimentation inhibitor (J) is preferably a polyethylene oxide-based wax. Examples of commercially available polyethylene oxide waxes include "Disparon 4200-20" and "Disparon 4200-20X" (all manufactured by Kusumoto Kasei Co., Ltd.).
In the antifouling coating composition of the present invention, the content of the antisettling agent (J) is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1 in the solid content of the antifouling coating composition. It is mass% or more and 5 mass% or less.

[Dehydrating agent (K)]
The antifouling coating composition of the present invention has excellent storage stability by using the hydrolyzable polymer (A) having good storage stability, but contains a dehydrating agent (K) if necessary. As a result, even better long-term storage stability can be obtained. Examples of the dehydrating agent (K) include synthetic zeolite, anhydrous gypsum, and hemihydrate gypsum (also known as roasted gypsum) as inorganic dehydrating agents, and tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane as organic dehydrating agents. , Tetraphenyloxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane and other alkoxysilanes, or condensates thereof, polyalkoxysilanes, methyl orthosilicate, ethyl orthosilicate and other alkyl esters of orthosilicate. Illustrated. The dehydrating agent (K) may be used alone or in combination of two or more.
The content of these dehydrating agents (K) in the antifouling coating composition is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.2% by mass, based on the solid content of the antifouling coating composition. It is 10% by mass or less, more preferably 0.3% by mass or more and 3% by mass or less.

[Solvent (L)]
The antifouling coating composition of the present invention is, if necessary, water or, for the purpose of improving the dispersibility of the hydrolyzable polymer (A) and the like, and adjusting the viscosity of the antifouling coating composition. A solvent (L) such as an organic solvent may be contained. The antifouling coating composition of the present invention may contain the solvent used when preparing the hydrolyzable polymer (A) as the solvent (L), or the hydrolyzable polymer (A). And, if necessary, a solvent added separately may be contained when mixing with other components. As the solvent (L), an organic solvent is preferable.
Examples of the organic solvent include aromatic organic solvents such as xylene, toluene, ethylbenzene, solvent naphtha and heavy aroma; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethanol, isopropyl alcohol, n-butanol, isobutanol and the like. Examples thereof include aliphatic (1 to 10 or less carbon atoms, preferably 2 to 5 or less) monohydric alcohols; ester solvents such as ethyl acetate and butyl acetate; and the like. The solvent (L) may be used alone or in combination of two or more.
The blending amount of the solvent (L) can be appropriately adjusted, but preferably, the total solid content of the antifouling coating composition of the present invention is 20% by mass or more and 90% by mass or less, more preferably 50 to 85% by mass. More preferably, the ratio is 55 to 80% by mass, and the amount of the solvent (L) added at the time of coating may be appropriately adjusted according to the workability.

[Other resins (M)]
In addition to the above-mentioned components, the antifouling coating composition of the present invention may contain a resin (M) other than the hydrolyzable polymer (A). These may be used alone or in combination of two or more.
Examples of such resins include chlorinated paraffin, acrylic resin containing no metal ester group, acrylic silicone resin, polyester resin, unsaturated polyester resin, fluororesin, polybutene resin, silicone rubber, polyurethane resin, epoxy resin, and the like. Polyamide resin, vinyl resin (vinyl chloride copolymer, ethylene / vinyl acetate copolymer, etc.), polyvinyl alkyl ether, rubber chloride, chlorinated olefin resin, styrene / butadiene copolymer resin, ketone resin, alkyd resin, kumaron resin , Terpenphenol resin, petroleum resin and other water-insoluble or sparingly water-soluble resins, and pineapple and other water-soluble resins can be used.
Among these, as the other resin (M), chlorinated paraffin and petroleum resin are preferable, and chlorinated paraffin is more preferable.

The chlorinated paraffin may have either a linear or branched molecular structure and may be liquid or solid (eg powder) under room temperature (eg 23 ° C.) conditions.
The average carbon number of chlorinated paraffin is preferably 8 or more and 30 or less, and more preferably 10 or more and 26 or less in one molecule. Such an antifouling coating composition containing chlorinated paraffin can form an antifouling coating film with few cracks and peeling. If the average carbon number is less than 8, the effect of suppressing the occurrence of cracks in the antifouling coating film may be insufficient, while if the average carbon number exceeds 30, the antifouling coating film is hydrolyzed. The property (renewability, cleanability) becomes small, and as a result, the antifouling property may be inferior.

Further, in chlorinated paraffin, the viscosity (unit poison, measurement temperature 25 ° C.) is preferably 1 or more and 500 or less, more preferably 1.2 or more and 100 or less, still more preferably 1.5 or more and 20 or less, and the specific gravity ( 25 ° C.) is preferably from 1.05 g / cm ³ or more 1.80 g / cm ³ or less, more preferably 1.10 g / cm ³ or more 1.70 g / cm ³ or less.
The chlorination rate (chlorine content) of the chlorinated paraffin is usually 35 parts by mass or more and 70 parts by mass or less, preferably 35 parts by mass or more and 65 parts by mass or less when the chlorinated paraffin is 100 parts by mass. An antifouling coating composition containing chlorinated paraffin having such a chlorination rate can form a coating film having few cracks, peeling and the like. Specific examples of such chlorinated paraffins include "Toyoparax 150" and "Toyoparax A-70" (both manufactured by Tosoh Corporation).

Examples of petroleum resins include C5 series, C9 series, styrene series, dichloropentadiene series, and hydrogenated additives thereof. Specific examples of petroleum resins include "Quinton 1500" and "Quinton 1700" (both manufactured by Nippon Zeon Corporation).

In the antifouling coating composition of the present invention, the content of the other resin (M) is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1 in the solid content of the antifouling coating composition. It is 5% by mass or more and 5% by mass or less.

[Manufacturing method of antifouling paint composition]
The composition of the present invention can be prepared by using the same devices, means and the like as known general antifouling paints. For example, after preparing the hydrolyzable polymer (A) in advance, the hydrolyzable polymer (A) (reaction solution), zinc oxide (B), monocarboxylic acid compound (C) and / or a metal ester thereof, The organic antifouling agent (D) and, if necessary, other components (E) to (M) may be added at once or sequentially, stirred and mixed for production.

[Anti-fouling coating film and base material with antifouling coating film, their manufacturing method, and antifouling method]
The antifouling coating film of the present invention is formed from the antifouling coating composition of the present invention, and is obtained by drying the antifouling coating composition.
Specifically, for example, an antifouling coating film can be obtained by applying the antifouling coating composition of the present invention onto an existing coating film or substrate and then drying (curing) the composition.
Examples of the method for applying the antifouling coating composition of the present invention include known methods such as a method using a brush, a roller, and a spray.
The antifouling coating composition applied by the above-mentioned method is, for example, under the condition of 25 ° C., preferably about 0.5 days or more and 7 days or less, more preferably 0.5 days or more and 5 days or less, still more preferably 0. A coating film can be obtained by drying by leaving it for 5 days or more and 3 days or less. The antifouling coating composition may be dried while being blown under heating.

The thickness of the antifouling coating film after drying is arbitrarily selected according to the polishing speed of the antifouling coating film and the period of use, but is preferably about 30 μm or more and 1,000 μm or less, for example. As a method for producing a coating film having this thickness, a method of applying the coating composition once to multiple times with a thickness of preferably 10 μm or more and 300 μm or less, more preferably 30 μm or more and 200 μm or less per application is used. Can be mentioned.

The base material with an antifouling coating film of the present invention is coated with an antifouling coating film formed by the antifouling coating composition, and has the antifouling coating film on the base material.
The method for producing the base material with an antifouling coating of the present invention is not particularly limited, and for example, the step (I) of applying or impregnating the base material with the antifouling coating composition of the present invention to obtain a coated body or an impregnated body. And it can be obtained by a production method having a step (II) of drying the coated body or the impregnated body.
As the method of applying the coating composition to the substrate in the step (I), the above-mentioned coating method can be adopted. Further, the method of impregnation is not particularly limited, and the impregnation method can be performed by immersing the base material in an amount of a coating composition sufficient for impregnation. Further, the method for drying the coated body or the impregnated body is not particularly limited, and the coated body or the impregnated body can be dried by the same method as the method for producing the antifouling coating film.

Further, the base material with an antifouling coating film of the present invention is a step (i) of forming a coating film formed by drying the antifouling coating composition of the present invention and a step (ii) of applying the coating film to the base material. ) Can also be obtained by a production method having.
The method for forming the coating film in the step (i) is not particularly limited, and the coating film can be produced by the same method as the method for producing the antifouling coating film.
The method of attaching the coating film to the base material in the step (ii) is not particularly limited, and for example, the coating film can be attached by the method described in JP2013-129724.

The antifouling method of the present invention uses an antifouling coating film formed by the antifouling coating composition of the present invention, and by coating the surface of the base material with the antifouling coating film, the base material is contaminated. Specifically, it suppresses the adhesion of aquatic organisms.
The antifouling coating composition of the present invention can be used in a wide range of industrial fields such as ships, fisheries, and marine structures to maintain the antifouling property of a base material for a long period of time. Such base materials include, for example, ships (container ships, large steel ships such as tankers, fishing boats, FRP ships, wooden ships, hull skins such as yachts, new ships or repair ships, etc.), fishing materials (ropes, fishing nets, etc.). , Fishing materials, floats, buoys, etc.), marine structures such as mega floats, etc. Among these, the base material is preferably selected from the group consisting of ships, underwater structures, and fishery materials, more preferably selected from the group consisting of ships and underwater structures, and is preferably ships. More preferred.
Further, the base material to which the antifouling coating composition of the present invention is formed on the surface has a surface treated with another treatment agent such as a rust inhibitor or some coating film such as a primer already formed on the surface. It may be overcoated on a surface already coated with the coating composition of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to such Examples. In the following, "part" means a mass part unless it is contrary to the purpose.

[Production of hydrolyzable polymer (A)]
In producing the hydrolyzable polymer (A), first, the hydrolyzable group-containing monomers (a1-1) and (a1-2) were prepared as follows.
<Preparation Example 1: Preparation of hydrolyzable group-containing monomer (metal ester group-containing monomer) (a1-1)>
85.4 parts by mass of propylene glycol monomethyl ether and 40.7 parts by mass of zinc oxide were placed in a reaction vessel equipped with a stirrer, condenser, thermometer, dropping device, nitrogen introduction tube, and heating / cooling jacket, and the temperature was 75 ° C. while stirring. The temperature was raised to. Subsequently, a mixture consisting of 43.1 parts by mass of methacrylic acid, 36.1 parts by mass of acrylic acid, and 5.0 parts by mass of water was added dropwise from the dropping device at a constant velocity over 3 hours. After completion of the dropping, the mixture was further stirred for 2 hours, and then 36.0 parts by mass of propylene glycol monomethyl ether was added to contain a hydrolyzable group-containing monomer (metal ester group-containing monomer) (a1-1). Obtained liquid.

<Preparation Example 2: Preparation of hydrolyzable group-containing monomer (metal ester group-containing monomer) (a1-2)>
72.4 parts by mass of propylene glycol monomethyl ether and 40.7 parts by mass of zinc oxide were placed in a reaction vessel equipped with a stirrer, condenser, thermometer, dropping device, nitrogen introduction tube, and heating / cooling jacket, and the temperature was 75 ° C. while stirring. The temperature was raised to. Subsequently, a mixture consisting of 30.1 parts by mass of methacrylic acid, 25.2 parts by mass of acrylic acid, and 51.6 parts by mass of versatic acid was added dropwise from the dropping device at a constant velocity over 3 hours. After completion of the dropping, the mixture was further stirred for 2 hours, and then 11.0 parts by mass of propylene glycol monomethyl ether was added to contain a hydrolyzable group-containing monomer (metal ester group-containing monomer) (a1-2). Obtained liquid.

<Production Example 1: Production of hydrolyzable polymer (metal ester group-containing copolymer) solution (A-1)>
15.0 parts by mass of propylene glycol monomethyl ether, 60.0 parts by mass of xylene, and 4.0 parts by mass of ethyl acrylate in a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction tube, and a heating / cooling jacket. The temperature was raised to 100 ± 5 ° C. with stirring. While maintaining the same temperature, 40.2 parts by mass of the reaction solution containing the metal ester group-containing monomer (a1-1) obtained in Preparation Example 1 and 15.0 parts by mass of methyl methacrylate in the reaction vessel from the dropping apparatus. Parts, 48.0 parts by mass of ethyl acrylate, 15.0 parts by mass of n-butyl acrylate, 2.5 parts by mass of polymerization initiator 2,2'-azobisisobutyronitrile, polymerization initiator 2,2'-azobis ( 2-Methylbutyronitrile) 6.5 parts by mass, chain transfer agent "Nofmer MSD" (α-methylstyrene dimer, manufactured by Nichiyu Co., Ltd.) 1.2 parts by mass, and xylene 10.0 parts by mass for 6 hours Dropped over. After completion of the dropwise addition, 0.5 parts by mass of the polymerization initiator tert-butylperoctate and 7.0 parts by mass of xylene were added dropwise over 30 minutes, and after further stirring for 1 hour and 30 minutes, 8.0 parts by mass of xylene was added. Then, a pale yellow transparent hydrolyzable polymer solution (A-1) containing a hydrolyzable polymer (copolymer containing a metal ester group) was prepared.
Table 1 shows the composition of the monomers used and the characteristic values of the hydrolyzable polymer solution (A-1) measured by the method described later.

<Production Example 2: Production of hydrolyzable polymer (metal ester group-containing copolymer) solution (A-2)>
15.0 parts by mass of propylene glycol monomethyl ether, 57.0 parts by mass of xylene and 4.0 parts by mass of ethyl acrylate in a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction tube, and a heating / cooling jacket. Was charged, and the temperature was raised to 100 ± 5 ° C. with stirring. While maintaining the same temperature, 52.0 parts by mass of the reaction solution containing the metal ester group-containing monomer (a1-1) obtained in Preparation Example 1 in the reaction vessel, methyl methacrylate 1.0, from the dropping device. 66.2 parts by mass of ethyl acrylate, 5.4 parts by mass of 2-methoxyethyl acrylate, 2.5 parts by mass of polymerization initiator 2,2'-azobisisobutyronitrile, 2,2'by mass of polymerization initiator -Azobis (2-methylbutyronitrile) 7.0 parts by mass, chain transfer agent "Nofmer MSD" (α-methylstyrene dimer, manufactured by Nichiyu Co., Ltd.) 1.0 parts by mass, and xylene 10.0 parts by mass. Was added dropwise over 6 hours. After completion of the dropwise addition, 0.5 parts by mass of the polymerization initiator tert-butyl peroctate (TBPO) and 7.0 parts by mass of xylene were added dropwise over 30 minutes, and after further stirring for 1 hour and 30 minutes, xylene was added to 4.4. A pale yellow transparent hydrolyzable polymer solution (A-2) containing a hydrolyzable polymer (copolymer containing a metal ester group) was prepared by adding parts by mass.
Table 1 shows the composition of the monomers used and the characteristic values of the hydrolyzable polymer solution (A-2) measured by the method described later.

<Production Example 3: Production of hydrolyzable polymer (metal ester group-containing copolymer) solution (A-3)>
10.0 parts by mass of propylene glycol monomethyl ether, 63.0 parts by mass of xylene, and 3.0 parts of ethyl acrylate in a reaction vessel equipped with a stirrer, condenser, thermometer, dropping device, nitrogen introduction tube, and heating / cooling jacket. Was charged, and the temperature was raised to 100 ± 5 ° C. with stirring. While maintaining the same temperature, 50.3 parts by mass of the reaction solution containing the metal ester group-containing monomer (a1-2) obtained in Preparation Example 2 and 9.0 parts by mass of methyl methacrylate in the reaction vessel from the dropping apparatus. 58.0 parts by mass of ethyl acrylate, 5.0 parts by mass of the polymerization initiator 2,2'-azobis (2-methylbutyronitrile) and 10.0 parts by mass of propylene glycol monomethyl ether were added dropwise over 4 hours. After completion of the dropwise addition, 0.5 parts by mass of the polymerization initiator tert-butyl peroctate and 7.0 parts by mass of xylene were added dropwise over 30 minutes, and after further stirring for 1 hour and 30 minutes, 12.0 parts by mass of xylene was added. Then, a pale yellow transparent hydrolyzable polymer solution (A-3) containing a hydrolyzable polymer (copolymer containing a metal ester group) was prepared.
Table 1 shows the composition of the monomers used and the characteristic values of the hydrolyzable polymer solution (A-3) measured by the method described later.

[Measurement of characteristic values of hydrolyzable polymer solution]
The method for measuring the characteristic values of the obtained hydrolyzable polymer solutions (A-1) to (A-3) is as follows.
<Viscosity of polymer solution>
The viscosity of the polymer solution at 25 ° C. was measured with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).

<Solid content>
In the present invention, the solid content refers to a heating residue when a mixture / composition or the like containing a solvent or the like is dried in a hot air dryer at 108 ° C. for 3 hours to volatilize the solvent or the like.

<Number average molecular weight (Mn) and weight average molecular weight (Mw) of hydrolyzable polymer>
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolyzable polymer were measured using GPC (gel permeation chromatography) under the following conditions.
GPC condition device: "HLC-8120 GPC" (manufactured by Tosoh Corporation)
Column: "TSKgel SuperH2000" and "TSKgel SuperH4000" are connected (both manufactured by Tosoh Corporation, inner diameter 6 mm / length 15 cm)
Eluent: tetrahydrofuran (THF)
Flow velocity: 0.500 ml / min
Detector: RI
Column constant temperature bath temperature: 40 ° C
Standard substance: Polystyrene Sample preparation method: A small amount of calcium chloride was added to the polymer solution prepared in each production example to dehydrate the polymer solution, and then the filtrate obtained by filtering with a membrane filter was used as a GPC measurement sample.

<Zinc content in hydrolyzable polymer solution>
The zinc content (mass%) in the hydrolyzable polymer solution was measured by an X-ray diffractometer (manufactured by Rigaku, sample horizontal multipurpose X-ray diffractometer Ultra IV).

[Examples 1 to 11 and Comparative Examples 1 to 7: Production of antifouling coating composition]
As shown in Table 2 below (note that the numerical values in the table indicate parts by mass), the hydrolyzable polymer composition obtained by the above production example, zinc oxide (B), monocarboxylic acid compound (C), and the like. An antifouling coating composition was produced by uniformly mixing the organic antifouling agent (D) and other components at room temperature using a paint shaker.
Each component used in Table 2 is as shown in Table 3.
The blending amount of each component shown in Table 2 indicates the blending amount in a solution or dispersion for the component having a solid content described in Table 3, and the component not having a solid content (excluding organic solvents). ) Indicates the amount of the solid content.

<Evaluation>
The obtained antifouling coating composition was evaluated as follows.
[Appearance of dry coating film]
Epoxy-based rust preventive paint (epoxy AC paint, trade name "Banno 500", manufactured by China Paint Co., Ltd.) is applied to a 70 x 200 x 3 mm sandblast plate so that its dry film thickness is about 150 μm, and then the paint is applied. An epoxy-based binder paint (trade name "Banno 500N", manufactured by China Paint Co., Ltd.) was applied onto the paint so that the dry film thickness was about 100 μm. On top of that, the antifouling coating composition of the above-mentioned Examples and Comparative Examples is coated once so that the dry film thickness is about 150 μm, and similarly applied repeatedly (antifouling) so that the dry film thickness is about 150 μm. The dry film thickness of the coating composition was 300 μm in total), dried at room temperature for 7 days, and then immersed in seawater at 40 ° C., and the appearance of the coating film such as the presence or absence of cracks was observed every month. The coating interval was 1 day / 1 coat.

[Standing antifouling test]
Epoxy rust preventive paint (epoxy AC paint, trade name "Banno 500", manufactured by China Paint Co., Ltd.) is applied to sandblasted steel plate (length 300 mm x width 100 mm x thickness 3.2 mm) with a dry film thickness of about 150 μm. After that, an epoxy-based binder paint (trade name "Banno 500N", manufactured by China Paint Co., Ltd.) was applied on the epoxy binder paint so that the dry film thickness was about 100 μm. Further, the antifouling coating composition of the above-mentioned Examples and Comparative Examples is applied once so that the dry film thickness is about 100 μm, and dried at room temperature for 7 days to obtain a test plate with an antifouling coating film. Made. In addition, all of the above-mentioned three coatings were set to 1 day / 1 coat.

The test plate prepared as described above was placed vertically in Nagasaki Bay, Nagasaki Prefecture, with 2/3 of the test plate submerged in seawater and 1/3 above the sea surface, and left to stand for 6 months. During the immersion, the area (%) of marine organisms adhering to the surface of the antifouling coating film was measured every month. The evaluation of the static antifouling property of the submerged part was evaluated according to the following evaluation criteria.

-Evaluation criteria for static antifouling property based on the area of marine organisms attached-
0: No attachment of marine organisms 0.5: Adhesion area of marine organisms exceeds 0% and 10% or less 1: Adhesion area of marine organisms exceeds 10% and 20% or less 2: Adhesion area of marine organisms More than 20% and less than 30% 3: The area of marine organisms is more than 30% and less than 40% 4: The area of marine organisms is more than 40% and less than 50% 5: The area of marine organisms is 50% Exceeds

[Discoloration of alternating dry and wet parts]
Using a color difference meter (Spectrophotometer "CM-3700A" manufactured by Konica Minolta), under the condition of C light source / field of view 2 °, the initial coating film of the test plate with antifouling coating film and the coating of the dry and wet alternating parts after 6 months of seawater immersion. The color difference (ΔE value) of the film was measured.
The ΔE value was calculated as an average value obtained by randomly measuring 10 points at a distance of 1 cm or more from the end of each test piece.
ΔE was calculated by the following formula from the values of L ^* , a ^* , and b ^* obtained by the spectrophotometer.
ΔE = {(L ^* _1- L ^* ₀ ) ² + (a ^* _1- a ^* ₀ ) ² + (b ^* _1- b ^* ₀ ) ² } ^1/2
Here, L ^* ₁ , a ^* ₁ , and b ^* ₁ represent L ^* , a ^* , and b ^* of the coating film of the wet and dry alternating portion after being immersed in seawater for 6 months, respectively, and L ^* ₀ , a ^* ₀ , and b ^*. ₀ represents L ^* , a ^* , and b ^* of the initial coating film, respectively.

[Damage resistance (dryness) of antifouling coating film]
Epoxy rust preventive paint (epoxy AC paint, trade name "Banno 500", manufactured by China Paint Co., Ltd.) is applied to a 70 x 150 x 1.6 mm sandblasted steel plate with a dry film thickness of 150 μm and an epoxy binder paint (brand name). The antifouling coating composition prepared by "Banno 500N", manufactured by China Paint Co., Ltd. with a dry film thickness of 100 μm in Examples and Comparative Examples was sprayed with an air spray so that the dry film thickness of the antifouling coating film was 150 μm. A test plate having a laminated antifouling coating film is prepared by applying at 1-day intervals, and the center on the antifouling coating film is formed 1 day, 3 days, and 5 days after the completion of coating of the antifouling coating film at a drying temperature of 23 ° C. Place a piece of wood of 30 x 30 x 10 mm on the part, apply a pressure of 40 kgf / cm ² (3.9 MPa) vertically from the top of the piece of wood for 20 minutes, and observe the state of the paint film surface (that is, deformation of the paint film). The degree was observed), and evaluation was performed based on the following evaluation criteria. A schematic view of the cross section of the coating film for each evaluation is shown in FIG. It is preferable that a coating film having excellent damage resistance can be obtained in a shorter number of drying days, and such an antifouling coating composition is excellent in drying property.
5: No deformation of the coating film 4: Slight deformation of the coating film is observed 3, 2, 1 shows considerable deformation, and the steel plate is partially exposed.
The degree of damage (deformation) increases in the order of 3, 2, and 1.
Results of the antifouling coating composition of each Example and Comparative Example, the appearance of the dry coating film in the antifouling property promotion test, the static antifouling property test, the discoloration of the dry-wet alternating part, and the damage resistance of the antifouling coating film. Is shown in Table 2.

In the antifouling coating compositions of Examples 1 to 11, the appearance of the antifouling coating film was excellent and no cracks were generated even in the antifouling property promotion test immersed in seawater at 40 ° C. In addition, good antifouling property was obtained in terms of static antifouling property. In addition, discoloration of the dry-wet alternating portion was suppressed, the drying property of the coating film was good, and the damage resistance of the coating film after coating was excellent.
On the other hand, in Comparative Example 2 in which the content of the monocarboxylic acid compound (C) and / or its metal ester in the solid content of the antifouling coating composition is less than 0.1% by mass and in Comparative Example 7 exceeding 10% by mass. In each case, in the antifouling property promotion test immersed in seawater at 40 ° C., cracks were generated in the antifouling coating film after the second month, and algae adhered to the cracked portion. In particular, in Comparative Example 7, the discoloration of the dry-wet alternating portion was remarkable, and the damage resistance of the antifouling coating film was also inferior.

Further, in Comparative Example 1 in which the content of zinc oxide (B) in the solid content of the antifouling coating composition was less than 55% by mass, the static antifouling property was inferior. Further, in Comparative Example 3 in which the content of zinc oxide (B) in the solid content of the antifouling coating composition exceeds 75% by mass, cracks occur from one month after being immersed in seawater at 40 ° C., and as a result, cracks occur. Algae adhered to the cracks.
In Comparative Examples 4 to 6 in which the content of the organic antifouling agent (D) in the solid content of the antifouling coating composition exceeds 10% by mass, all of them are one month when the dry coating film is immersed in seawater at 40 ° C. Cracks occurred from the eyes or the second month, and the appearance became inferior. In addition, with the occurrence of cracks, algae adhered to the cracked portion, and the static antifouling property was also inferior. Further, the discoloration of the dry-wet alternating portion was remarkable, and in particular, the discoloration was remarkable in Comparative Examples 4 and 5 containing the pyrithion compound. On the other hand, in Comparative Example 6, the damage resistance of the antifouling coating film was inferior, and sufficient damage resistance could not be obtained even after 5 days of drying.

Claims (11)

1. Antifouling coating composition containing a hydrolyzable polymer (A) containing a metal ester group, zinc oxide (B), a monocarboxylic acid compound (C) and / or a metal ester thereof, and an organic antifouling agent (D). It ’s a thing,
   The content of zinc oxide (B) in the solid content of the antifouling coating composition is 55% by mass or more and 75% by mass or less.
   The content of the monocarboxylic acid compound (C) and / or its metal ester in the solid content of the antifouling coating composition is 0.1% by mass or more and 10% by mass or less.
   The content of the organic antifouling agent (D) in the solid content of the antifouling coating composition is 10% by mass or less.
   Antifouling paint composition.
2. The antifouling coating composition according to claim 1, wherein the metal ester group contained in the hydrolyzable polymer (A) is represented by the following formula (1).
   

   

   
   (In formula (1), M indicates copper or zinc, and * indicates the bonding position.)
3. The hydrolyzable polymer (A) is a polymer (A1) having a structural unit derived from a polymerizable compound represented by the following formula (1-1) and a polymerizable polymer represented by the following formula (1-2). The antifouling coating composition according to claim 1 or 2, which contains at least one selected from the group consisting of a polymer (A2) having a structural unit derived from a compound.
   

   

   
   (In formula (1-1), R ¹¹ independently represents a monovalent group containing a terminal ethylenically unsaturated group, and M represents copper or zinc.)
   

   

   
   (In the formula (1-2), R ²¹ represents a monovalent group containing a terminal ethylenically unsaturated group, and R ²² is a monovalent group having 1 to 30 carbon atoms and not containing a terminal ethylenically unsaturated group. Indicates an organic group, where M indicates copper or zinc.)
4. The hydrolyzable polymer (A) is represented by a polymer (A1') having a structural unit derived from a polymerizable compound represented by the following formula (1-1') and a following formula (1-2'). The antifouling coating composition according to any one of claims 1 to 3, which contains at least one selected from the group consisting of a polymer (A2') having a structural unit derived from a polymerizable compound.
   

   

   
   (In formula (1-1'), R ¹² independently represents a hydrogen atom or a methyl group, and M represents copper or zinc.)
   

   

   
   (In the formula (1-2'), R ²³ represents a hydrogen atom or a methyl group, R ²⁴ represents a monovalent organic group having 1 to 30 carbon atoms and containing no terminal ethylenically unsaturated group, and M represents a monovalent organic group. Indicates copper or zinc.)
5. The antifouling coating composition according to any one of claims 1 to 4, wherein the organic antifouling agent (D) is an organic antifouling agent excluding a pyrithion compound.
6. The organic antifouling agent (D) is 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, (+/-) -4- [1-]. (2,3-Dimethylphenyl) Ethyl] -1H-imidazole, and at least one selected from the group consisting of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one. The antifouling coating composition according to 5.
7. An antifouling coating film formed from the antifouling coating composition according to any one of claims 1 to 6.
8. A base material with an antifouling coating film coated with the antifouling coating film according to claim 7.
9. The base material with an antifouling coating film according to claim 8, wherein the base material is selected from the group consisting of ships, underwater structures, and fishery materials.
10. A step (I) of applying or impregnating the base material with the antifouling coating composition according to any one of claims 1 to 6 to obtain a coated body or an impregnated body, and a step of drying the coated body or the impregnated body. Have (II),
    A method for manufacturing a base material with an antifouling coating film.
11. A step (i) of forming an antifouling coating film formed by drying the antifouling coating composition according to any one of claims 1 to 6, and a step of attaching the antifouling coating film to a substrate (ii). )
    A method for manufacturing a base material with an antifouling coating film.

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