JP2021155728A - Antifouling coating composition - Google Patents

Abstract

To provide an antifouling coating composition which comprises a silyl ester based polymer which has excellent storage stability and can form an antifouling coating film having excellent crack resistance, adhesiveness to a deteriorated film and dynamic antifouling properties and medetomidine.SOLUTION: There is provided an antifouling coating composition which comprises a silyl ester based polymer (A) having a structural unit (a-1) derived from a polymerizable monomer (a1) represented by the formula (a1), an acrylic polymer (B) having a structural unit (b-1) derived from glycidyl (meth)acrylate, medetomidine (C) and cuprous oxide (D), wherein the content of the cuprous oxide (D) is more than 0 mass% and 55 mass% or less in the solid content of the antifouling coating composition. R1-CH=C(CH3)-COO-(SiR2R3O)n-SiR4R5R6 (a1) [wherein, R2 to R6 each independently is a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom, n is an integer of 0 or 1 or more, R1 is a hydrogen atom or a group represented by R7-O-C(=O)- and R7 is a hydrogen atom or the like.]SELECTED DRAWING: None

Description

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

A wide variety of aquatic organisms are found on the surface of base materials (ships, underwater structures, fishing nets, seawater water supply and drainage pipes of factories, etc.) that are exposed to water (oceans, rivers, lakes, etc.) for a long time in the natural environment. Easy to adhere. When aquatic organisms adhere to the surface of the base material, they spoil the appearance and cause various problems. For example, when the base material is a ship, the resistance due to the water flow increases, which may lead to a decrease in ship speed and an increase in fuel consumption. When the base material is an underwater structure, the anticorrosion coating film applied to the surface of the base material may be damaged, resulting in damages such as a decrease in strength and function and a significant shortening of life. When the base material is a fishing net such as an aquaculture net or a fixed net, the mesh may be blocked by aquatic organisms, which may cause serious problems such as oxygen deficiency lethal of the aquaculture organism and the fished organism. If aquatic organisms adhere to and propagate in the water supply and drainage pipes of seawater in factories, thermal power plants, nuclear power plants, etc., they may cause blockage of the water supply and drainage pipes and decrease in flow velocity.

In order to prevent the adhesion of aquatic organisms that cause such defects, an antifouling paint is usually applied to the surface of the base material to form an antifouling coating film. Among these antifouling paints, hydrolyzable antifouling paints are widely used because of their advantages such as excellent antifouling performance, and one of them is the development of antifouling paints containing a silyl ester polymer. It has been advanced.

Patent Document 1 describes an antifouling coating composition containing a silyl ester copolymer containing triisopropylsilylmethacrylate and a hydrophilic (meth) acrylate comonomer, and medetomidine.
Patent Document 2 describes an antifouling coating composition in which a copolymer containing a structural unit derived from styrene and a structural unit derived from glycidyl (meth) acrylate is blended with an antifouling coating material containing a silyl ester-based polymer. The thing is listed.

Special Table 2019-535868 International Publication No. 2014/175246

Patent Document 1 discloses that the antifouling coating composition can form a coating film having cracking resistance and excellent antifouling properties, particularly excellent barnacle adhesion inhibitory properties. However, in the examples of the document, although the barnacle resistance by the static immersion test was evaluated as the antifouling performance, the dynamic antifouling property was unknown. Furthermore, according to the studies by the present inventors, the antifouling coating film formed from the antifouling coating composition containing medetomidine has crack resistance, and is a conventional antifouling coating film that has deteriorated by being immersed in seawater or the like (hereinafter referred to as “foul coating film”). It has been found that it is difficult to form an antifouling coating film having excellent adhesion to (simply referred to as a deteriorated coating film) and dynamic antifouling property. Furthermore, it was found that the antifouling coating composition has room for improvement from the viewpoint of long-term storage stability.

An object of the present invention is to use a silyl ester polymer and medetomidine, which can form an antifouling coating film having excellent crack resistance, adhesion to a deteriorated coating film, and dynamic antifouling property, and also have excellent storage stability. It is an object of the present invention to provide an antifouling coating composition containing.

The present inventor has carried out diligent research to solve the above problems, and found that the antifouling coating composition described below can solve the above problems. That is, the present invention relates to the following [1] to [10].

[1] A silyl ester-based polymer (A) having a structural unit (a-1) derived from the polymerizable monomer (a1) represented by the formula (a1), and a structure derived from glycidyl (meth) acrylate. An antifouling coating composition containing an acrylic polymer (B) having a unit (b-1), medetomidine (C), and cuprous oxide (D).
An antifouling coating composition in which the content of the cuprous oxide (D) is more than 0% by mass and 55% by mass or less in the solid content of the antifouling coating composition.
R ¹ −CH = C (CH ₃ ) −COO− (SiR ² R ³ O) _{n −} ^{SiR 4} R ⁵ R ⁶ … (a1)
[In the formula (a1), R ^{2 to} R ⁶ are monovalent organic groups having 1 to 20 carbon atoms which may independently have heteroatoms. n is an integer greater than or equal to 0 or 1. R ¹ is a hydrogen atom or ^{a group represented by R 7} −OC (= O) −, and R ⁷ is a monovalent group having 1 to 20 carbon atoms which may have a hydrogen atom or a hetero atom. It is an organic group or a silyl group represented by ^{R 8} R ⁹ R ^{10 Si−, and R 8} , R ⁹ and R ¹⁰ are monovalents having 1 to 20 carbon atoms which may independently have heteroatoms. It is an organic group of. ]

[2] The antifouling coating composition according to the above [1], which further contains the monocarboxylic acid compound (E).
[3] The antifouling coating composition according to the above [2], wherein the monocarboxylic acid compound (E) is a rosin (E1).

[4] Mass ratio of the rosins (E1) to the total of the silyl ester polymer (A) and the acrylic polymer (B) (total mass of the polymer (A) and the polymer (B)). / The antifouling coating composition according to the above [3], which has a mass ratio of rosins (E1) of 0.7 to 4.
[5] The antifouling coating material according to any one of [1] to [4] above, which further contains talc and has a talc content of 2 to 17% by mass in the solid content of the antifouling coating composition. Composition.

[6] The antifouling coating composition according to any one of [1] to [5] above, which is used for repairing a deteriorated coating film of an antifouling coating film.

[7] An antifouling coating film formed from the antifouling coating composition according to any one of the above [1] to [6].
[8] A base material with an antifouling coating film having the base material and the antifouling coating film according to the above [7] provided on the surface of the base material.

[9] The base material with an antifouling coating film according to the above [8], wherein the base material is at least one selected from ships, underwater structures, fishery materials, and water supply and drainage pipes.
[10] A method for producing a base material with an antifouling coating film, which comprises a step of applying or impregnating the base material with the antifouling coating composition according to any one of the above [1] to [6].

According to the present invention, a silyl ester-based polymer and medetomidine, which can form an antifouling coating film having excellent crack resistance, adhesion to a deteriorated coating film, and dynamic antifouling property, and have excellent storage stability, are used. An antifouling coating composition containing the above is provided.

Hereinafter, embodiments of the present invention will be described in detail.
Each component described herein can be used alone or in combination of two or more.
The term "polymer" is used to include homopolymers and copolymers.
"(Meta) acrylate" is a general term for acrylate and methacrylate. The same applies to the examples of (meth) acrylic acid and the like.

"Structural unit derived from XX" means that XX is A ¹ A ² C = CA ³ A ⁴ (C = C is a polymerizable carbon-carbon double bond, and A ^{1 to} A ⁴ are bonded to carbon atoms, respectively. It is a structural unit represented by the following formula, for example.

[Anti-fouling paint composition]
The antifouling coating composition of the present embodiment (hereinafter, also referred to as “composition (I)”) includes a silyl ester-based polymer (A), an acrylic-based polymer (B), and medetomidine, which will be described below, respectively. It contains C) and cuprous oxide (D).

<Cyril ester polymer (A)>
The silyl ester-based polymer (A) (hereinafter, also referred to as “polymer (A)”) has a structural unit (a-1) derived from the polymerizable monomer (a1) represented by the formula (a1). ..
R ¹ −CH = C (CH ₃ ) −COO− (SiR ² R ³ O) _{n −} ^{SiR 4} R ⁵ R ⁶ … (a1)
Each symbol in the formula (a1) will be described below.
R ^{2 to} R ⁶ are monovalent organic groups having 1 to 20 carbon atoms which may independently have heteroatoms. Examples of the organic group include a linear or branched alkyl group, a cycloalkyl group, and an aryl group in which a hetero atom such as an oxygen atom may intervene between carbon atoms and carbon atoms, and crack resistance is provided. From the viewpoint of easily obtaining an excellent coating film with a good balance of long-term dynamic antifouling property due to its properties and appropriate hydrolyzability, it is preferably selected from a linear or branched alkyl group having 1 to 8 carbon atoms and a phenyl group. At least one selected, more preferably a branched alkyl group.

Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group and a 2-ethylhexyl group. It is preferably an isopropyl group.

n is 0 or an integer greater than or equal to 1, preferably 0. The upper limit of n may be, for example, 50.
R ¹ is a hydrogen atom or ^{a group represented by R 7} −OC (= O) −, and is preferably a hydrogen atom. R ⁷ is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom, or a silyl group represented by ^{R 8} R ⁹ R ^{10 Si−.} R ⁸ , R ⁹ and R ¹⁰ are monovalent organic groups having 1 to 20 carbon atoms which may independently have heteroatoms. Examples of the monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom include the above-mentioned specific examples.

As the polymerizable monomer (a1), trialkylsilyl methacrylate, alkyldiarylsilylmethacrylate and aryldialkylsilylmethacrylate are preferable, and trialkylsilylmethacrylate is more preferable. Examples of the trialkylsilyl methacrylate include trimethylsilylmethacrylate, triethylsilylmethacrylate, tripropylsilylmethacrylate, triisopropylsilylmethacrylate, tributylsilylmethacrylate, triisobutylsilylmethacrylate, tri-sec-butylsilylmethacrylate, and tri2-ethylhexylsilylmethacrylate. Butyldiisopropylsilylmethacrylate can be mentioned. Further, as the polymerizable monomer (a1), a polymerizable monomer having n or more 2 in the above formula (a1) such as 1-methacryloyloxynonamethyltetrasiloxane can also be mentioned. Among these, trialkyl having a branched alkyl group can be easily obtained from the viewpoint of easily obtaining an excellent antifouling coating film having a good balance of long-term dynamic antifouling property having crack resistance and appropriate hydrolyzability. Cyril methacrylate is preferred, and triisopropylsilyl methacrylate is particularly preferred.

The structural unit (a-1) may be one type or two or more types.
The polymer (A) can further have a structural unit (a-2) derived from another ethylenically unsaturated monomer (hereinafter, also referred to as “monomer (a2)”).

Examples of the monomer (a2) include a polymerizable monomer (a11) represented by the formula (a11).
R ¹ −CH = CH −COO− (SiR ² R ³ O) _n ^{− SiR 4} R ⁵ R ⁶ … (a11)
Wherein (a11), R ¹ ~R ⁶ and n are as defined the same symbols in the formula (a1).

Examples of the polymerizable monomer (a11) include trialkylsilyl acrylates, alkyldiarylsilyl acrylates and aryldialkylsilyl acrylates. Examples of the trialkylsilyl acrylate include trimethylsilyl acrylate, triethylsilyl acrylate, tripropylsilyl acrylate, triisopropylsilyl acrylate, tributylsilyl acrylate, triisobutylsilylacrylate, tri-sec-butylsilylacrylate, and tri2-ethylhexylsilylacrylate. Butyl diisopropyl silyl acrylate can be mentioned. Further, as the polymerizable monomer (a11), a polymerizable monomer having n or more 2 in the above formula (a11) such as 1-acryloyloxynonamethyltetrasiloxane can also be mentioned.

From the viewpoint of crack resistance (water resistance) of the antifouling coating film, the polymerizable monomer represented by the formula (a11) is not used, and the polymerizable monomer represented by the formula (a1) is not used. It is preferable to use (a1).

As the monomer (a2), for example,
(Meta) acrylic acid;
(Meta) acrylic acid esters (excluding polymerizable monomers (a1) and (a11)), specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl. (Meta) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2 -Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate;
Alicyclic (meth) acrylates such as cyclohexyl (meth) acrylates;
Aromatic ring-containing (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;
Methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxypropyl (Meta) acrylate, propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, isobutoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. Alkoxyalkyl (meth) acrylate or allyloxyalkyl (meth) acrylate;
Glycol-based (meth) acrylates such as ethoxy-diethylene glycol (meth) acrylate, methoxy-triethylene glycol (meth) acrylate, and methoxy-dipropylene glycol (meth) acrylate;
Vinyl-based monomers, specifically vinyl acetate, isobutyl vinyl ether, styrene, vinyltoluene, (meth) acrylonitrile, vinyl propionate, vinyl benzoate;
Metal ester group-containing (meth) acrylates, specifically zinc (meth) acrylates, zinc di (meth) acrylates, copper (meth) acrylates, and copper di (meth) acrylates can also be mentioned.

Among the monomers (a2), alkyl (meth) acrylates, alicyclic-containing (meth) acrylates, alkoxyalkyl (meth) acrylates and glycol-based (meth) acrylates are preferable, and alkyl (meth) acrylates and alkoxyalkyl (meth) acrylates are preferable. Acrylate is more preferred.

The structural unit (a-2) may be one type or two or more types.
The ratio of the structural unit (a-1) in the polymer (A) is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and preferably 80% by mass or less. It is preferably 75% by mass or less, more preferably 70% by mass or less.

The ratio of the structural unit (a-2) in the polymer (A) is preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, and preferably 65% by mass or less. It is preferably 60% by mass or less, more preferably 55% by mass or less.

When the ratio of each structural unit is within the above range, the antifouling coating film formed from the composition (I) has an appropriate hydrolyzability and tends to be excellent in antifouling property for a long period of time. The ratio of each structural unit can be determined by NMR (nuclear magnetic resonance spectroscopy), Pyro-GC / MS (pyrolysis gas chromatograph mass spectrometry), or the like.

The weight average molecular weight (Mw) of the polymer (A) is preferably 3,000 or more, more preferably 10,000 or more, from the viewpoint of improving the crack resistance of the antifouling coating film formed from the composition (I). It is preferably 70,000 or less, more preferably 50,000 or less. Mw can be determined by gel permeation chromatography (GPC) measurement or an equivalent method under the conditions adopted in the examples described later.
The polymer (A) may be used alone or in combination of two or more.

<Acrylic polymer (B)>
The coating film containing the hydrolyzable silyl ester polymer (A) and medetomidine (C) dissolves at a constant rate in seawater for a certain period from the initial stage of immersion, but the hydrolysis inside the coating film progresses. As a result, the water resistance of the coating film is lowered, and cracks and peeling may occur. To solve this problem, when the following specific acrylic polymer (B) is blended with the silyl ester polymer (A), the crack resistance can be improved while maintaining the dynamic antifouling property of the coating film. can.

The acrylic polymer (B) (hereinafter, also referred to as “polymer (B)”) has a structural unit (b-1) derived from glycidyl (meth) acrylate. The structural unit (b-1) contributes to the improvement of the dynamic antifouling property of the antifouling coating film formed from the composition (I) and the adhesiveness to the deteriorated coating film.

The structural unit (b-1) may be one type or two types.
The ratio of the structural unit (b-1) in the acrylic polymer (B) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 40% by mass or less. , More preferably 30% by mass or less, further preferably 25% by mass or less, and particularly preferably 15% by mass or less. When the ratio of the structural unit (b-1) is equal to or higher than the above lower limit value, the antifouling coating film has high dynamic antifouling property and adhesiveness to the deteriorated coating film, and the antifouling coating composition is a pigment described later. Is preferable because sufficient dispersibility of the pigment can be obtained. When the ratio of the structural unit (b-1) is not more than the above upper limit value, the antifouling property is high, which is preferable. Further, the composition tends to be more excellent in storage stability when the proportion of the structural unit (b-1) is in a particularly preferable range.
The acrylic polymer (B) preferably further has a structural unit (b-2) derived from an aromatic vinyl compound.

The structural unit (b-2) has a phenyl group, which is a hydrophobic functional group, and contributes to the improvement of crack resistance of the antifouling coating film formed from the composition (I), as well as the coating film hardness. Contributes to improvement of impact resistance and sweepability. Although the reason for the improved sweepability is not clear, the structural unit (b-2) improves the coating film hardness of the antifouling coating film to be formed and is physically resistant to external forces such as frictional resistance in water. It is presumed that a good sweeping property is exhibited.

Examples of the aromatic vinyl-based compound include styrene-based compounds such as styrene, methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, and monochlorostyrene, and styrene is preferable among these.

The structural unit (b-2) may be one type or two or more types.
The ratio of the structural unit (b-2) in the acrylic polymer (B) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 80% by mass or less. , More preferably 75% by mass or less, still more preferably 70% by mass or less. When the ratio of the structural unit (b-2) is at least the above lower limit value, the antifouling coating film has high crack resistance and impact resistance, which is preferable. When the ratio of the structural unit (b-2) is not more than the above upper limit value, the hydrophobicity of the antifouling coating film is not too high and the hydrolysis of the polymer (A) is not hindered, so that the antifouling property is excellent.

The acrylic polymer (B) can further have a structural unit (b-3) derived from another ethylenically unsaturated monomer (hereinafter, also referred to as “monomer (b3)”).
As the monomer (b3), for example,
(Meta) acrylic acid;
(Meta) acrylic acid esters (excluding glycidyl (meth) acrylate), specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl ( Meta) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Alkyl (meth) acrylates such as 3,5,5-trimethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, and stearyl (meth) acrylate;
Alicyclic (meth) acrylates such as cyclohexyl (meth) acrylates;
Aromatic ring-containing (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;
Methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxypropyl (Meta) acrylate, propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, isobutoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. Alkoxyalkyl (meth) acrylate or allyloxyalkyl (meth) acrylate;
Glycol-based (meth) acrylates such as ethoxy-diethylene glycol (meth) acrylate, methoxy-triethylene glycol (meth) acrylate, and methoxy-dipropylene glycol (meth) acrylate;
Epoxy group-containing (meth) acrylate other than glycidyl (meth) acrylate;
Polyfunctional (meth) acrylates, specifically, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol. Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol propane tri (meth) acrylate, di (trimethylol propane) Tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate;
Vinyl-based monomers (excluding aromatic vinyl-based compounds), specific examples thereof include vinyl acetate, isobutyl vinyl ether, (meth) acrylonitrile, vinyl propionate, and vinyl benzoate.

Among these, (meth) acrylic acid esters are preferable, alkyl (meth) acrylates are more preferable, and methyl (meth) acrylates and butyl (meth) acrylates are even more preferable.

The structural unit (b-3) may be one type or two or more types.
By changing the type or amount of the structural unit (b-3), the viscosity and glass transition temperature of the acrylic polymer (B), the hardness of the antifouling coating film, and the like can be adjusted.

The ratio of the structural unit (b-3) in the acrylic polymer (B) is preferably 89% by mass or less, more preferably 82% by mass or less, still more preferably 75% by mass or less.
The ratio of each structural unit can be determined by the same method as for the silyl ester-based polymer (A).

The weight average molecular weight (Mw) of the acrylic polymer (B) is preferably 2,000 or more, more preferably 5, from the viewpoint of improving the crack resistance of the antifouling coating film formed from the composition (I). It is 000 or more, preferably 50,000 or less, and more preferably 30,000 or less. Mw can be determined by gel permeation chromatography (GPC) measurement or an equivalent method under the conditions adopted in the examples described later.
The acrylic polymer (B) can be used alone or in combination of two or more.

The content of the acrylic polymer (B) in the composition (I) is preferably 5 parts by mass or more with respect to 100 parts by mass of the silyl ester polymer (A), and the antifouling coating film has crack resistance and deterioration. From the viewpoint of further improving the adhesion to the coating film, the dynamic antifouling property of the antifouling coating film is more preferably 15 parts by mass or more, further preferably 20 parts by mass or more, preferably 200 parts by mass or less. From the point of improvement, it is more preferably 130 parts by mass or less, still more preferably 110 parts by mass or less.

The total content of the silyl ester-based polymer (A) and the acrylic-based polymer (B) is preferably 5% by mass or more, more preferably 5% by mass or more, based on 100% by mass of the total solid content of the composition (I). It is 10% by mass or more, preferably 30% by mass or less, and more preferably 25% by mass or less. When the total content is in this range, an antifouling coating film having excellent crack resistance can be easily obtained.

The solid content in the composition (I) is preferably 50% by mass or more, more preferably 60% by mass or more, preferably 95% by mass or less, and more preferably 90% by mass or less.

In the present specification, the solid content of the composition (I) and its content are the heating residue (nonvolatile content) obtained by the following method or an equivalent method and its content. Weigh the composition (I) on a metal test dish of known mass and spread it evenly on the bottom surface. It is heated in a hot air dryer at a temperature of 105 to 110 ° C. for 3 hours to remove volatile components. After taking out and cooling to room temperature (example: 23 ° C.), the mass of the obtained non-volatile component (heating residue) is weighed, and the content rate of the solid content (heating residue) is calculated from the following formula.
Content of solid content (heated residue) (%) = heated residue (g) x 100 / mass (g) of the weighed composition (I)
The same applies to the solid content of each component and its content.

<Method for producing polymer>
The method for producing the polymer (A) and the polymer (B) is not particularly limited, and examples thereof include solution polymerization, suspension polymerization, and pressure polymerization, and are generally used in terms of high versatility. Solution polymerization performed under normal pressure using a suitable organic solvent is preferable. Examples of the solution polymerization include production by the following procedure.

The solvent is charged in a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction tube and a heating / cooling jacket, and heating and stirring are performed under a temperature condition of about 60 to 200 ° C. under a nitrogen stream. While maintaining the same temperature, the above-mentioned monomers, the polymerization initiator, and if necessary, a mixture of a solvent and a chain transfer agent were added dropwise from the dropping device so as to preferably have the ratio of the structural units described above. The polymer (A) or the polymer (B) can be obtained by carrying out the polymerization reaction.

The polymerization initiator is not particularly limited, and various radical polymerization initiators can be used. Specifically, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 4 , 4'-azobis-4-cyanovaleric acid, benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, tert-butylperoxyoctate, tert-butylperoxybenzoate, potassium persulfate, excess Examples thereof include sodium sulfate. 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 polymer (A) or the polymer (B) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of each of the above-mentioned monomers (reaction raw materials). More preferably, 0.5 to 5 parts by mass.

Examples of the solvent that can be used for producing the polymer (A) or the polymer (B) include organic solvents and water. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, mesitylene, and coltarnaphtha; alcohol solvents such as ethanol, propanol, isopropyl alcohol, butanol, and isobutanol; propylene glycol monomethyl ether, and di. Ether-based solvents such as propylene glycol monomethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone and cyclohexanone; ester-based solvents such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate can be mentioned.

The chain transfer agent is not particularly limited, and is, for example, α-methylstyrene dimer, thioglycolic acid, diterpen, turpinolene, γ-terpinene; mercaptans such as tert-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, chloride. Halides such as methylene, bromoform and bromotrichloroethane; secondary alcohols such as isopropanol and glycerin can be mentioned.

When a chain transfer agent is used in the production of the silyl ester-based polymer (A), the amount used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass in total of each of the above-mentioned monomers (reaction raw materials).

<Medetomidine (C)>
Medetomidine (C) is a compound represented by the following formula (c1), (+/-)-4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole, and has an optical isomer. However, it may be only one of them or a mixture of any ratio.

In addition, the composition (I) may use an adduct to an imidazolium salt, a metal, or the like as a part or all of medetomidine. In this case, as a raw material for preparing the composition (I), an adduct to an imidazolium salt, a metal, or the like may be used, and the composition (I) or an antifouling formed from the composition (I) is formed. An adduct to an imidazolium salt, a metal, or the like may be formed in the coating film.

The conventional antifouling coating composition that does not contain an acrylic polymer has insufficient adhesion to a deteriorated coating film such as a zinc acrylic resin-based antifouling coating film containing rosins, and is directly coated. Was difficult. In response to this problem, the composition (I) can greatly improve the adhesiveness to the deteriorated coating film while maintaining the dynamic antifouling property. Further, when the antifouling coating composition for repair is directly applied to the deteriorated coating film, the surface roughness of the formed antifouling coating film tends to increase due to the surface roughness of the deteriorated coating film. Physically aquatic organisms are more likely to adhere. Since the composition (I) contains medetomidine (C), an antifouling coating film having excellent antifouling properties can be formed even if it is directly applied to the deteriorated coating film as described above. That is, it can be said that the composition (I) is suitable for repair coating and repair applications for deteriorated coating films. Here, the deteriorated coating film means a coating film (used coating film) that is actually immersed in seawater or fresh water for a certain period of time (for example, 30 weeks or more, preferably 50 weeks or more).

Examples of the antifouling coating film (deteriorated coating film) to be repaired include a zinc acrylic resin-based antifouling coating film and a silyl resin-based antifouling coating film, and an antifouling coating film containing rosins is particularly preferable. A zinc-acrylic resin-based antifouling coating film containing rosins is more preferable because the problem of adhesion is better solved.

The antifouling coating film containing rosins is an antifouling coating film usually containing 0.5 to 40% by mass of rosins in the antifouling coating film, and can further exert the effect of the present invention. From the viewpoint, it is preferably 1 to 30% by mass, more preferably 1.5 to 15% by mass. In the antifouling coating film, for example, rosins are usually 0.5 to 40% by mass, preferably 1 to 30% by mass, and more preferably 1.5 to 15% by mass with respect to 100% by mass of the solid content of the composition. It is formed by an antifouling coating composition containing mass%. Examples of rosins include specific examples listed as rosins (E1) described later.

The content of medetomidin (C) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 2% by mass or less, based on 100% by mass of the solid content of the composition (I). It is more preferably 1% by mass or less, further preferably 0.5% by mass or less, and particularly preferably 0.15% by mass or less. The content of medetomidin (C) in the composition (I) is preferably 0.1 part by mass or more with respect to 100 parts by mass in total of the silyl ester polymer (A) and the acrylic polymer (B). , More preferably 0.3 parts by mass or more, further preferably 0.5 parts by mass or more, preferably 5 parts by mass or less, more preferably 4 parts by mass or less, still more preferably 3 parts by mass or less, and particularly preferably 1 part or less. It is less than a part by mass. When the content of medetomidine (C) is in this range, the antifouling coating film formed from the composition (I) exhibits more excellent antifouling property. Furthermore, when the content of medetomidine (C) is in a particularly preferable range, the composition (I) exhibits better storage stability.

<Copper oxide (D)>
The antifouling coating composition containing the silyl ester polymer (A) and medetomidine (C) contains cuprous oxide (D), and thus aquatic plant species such as algae represented by slime and sea lettuce. It is possible to improve the dynamic antifouling property against living organisms.

The content of the cuprous oxide (D) is more than 0% by mass and 55% by mass or less, preferably 10 to 53% by mass, and more preferably 20 to 52% by mass in the solid content of the antifouling coating composition. be. When the content of cuprous oxide (D) is at least the above lower limit value, the dynamic antifouling property of the antifouling coating film formed is improved, and when it is at least the above upper limit value, the composition (I) is The long-term storage stability is excellent, and the dynamic antifouling property of the formed antifouling coating film is improved.

Although the mechanism of action that exerts the above effects is not clear, for example, antifouling coating compositions containing a silyl ester-based polymer (A), medetomidin (C), and copper (D) in excess of a specific amount are described. It is presumed that the molecular weight of the silyl ester-based polymer (A) is significantly increased due to the interaction of the components and the viscosity of the coating composition is increased. Since the amount of copper (D) oxide is less than a specific amount, it is presumed that this increase in viscosity is suppressed and the long-term storage stability is improved. Similarly, although the mechanism of action is not clear, the antifouling coating composition contains the silyl ester-based polymer (A) and the polymer (B) and contains less than a specific amount of cuprous oxide (D). It is presumed that the substance (I) moderately increases the consumption rate of the coating film due to the interaction of these components, and the dynamic antifouling property of the plant species against aquatic organisms is improved.

The cuprous oxide (D) preferably has an average particle size of about 1 to 30 μm, and includes those having an average particle size of 2 to 10 μm from the viewpoint of improving the antifouling property and water resistance of the antifouling coating film to be formed. Is more preferable.
As the cuprous oxide (D), those surface-treated with glycerin, stearic acid, lauric acid, sucrose, lecithin, mineral oil and the like are used from the viewpoint of long-term stability of the composition (I) during storage. preferable.

As such cuprous oxide (D), commercially available ones can be used, for example, NC-301 (average particle size: 2 to 4 μm) and NC-803 (average) manufactured by NC Tech Co., Ltd. Particle size: 6-10 μm), AMERICAN CHEMET Co., Ltd. Red Copp97N Premium, Purple Copp, LoLoTint97, etc.

<Monocarboxylic acid compound (E)>
The composition (I) preferably contains the monocarboxylic acid compound (E) from the viewpoints of not only improving the antifouling property but also adjusting the consumption rate of the coating film.
Examples of the monocarboxylic acid compound (E) include aliphatic or alicyclic monocarboxylic acids, monocarboxylic acid derivatives thereof, or metal salts thereof. Examples of the monocarboxylic acid derivative include esters and amides of monocarboxylic acids. Examples of the metal salt include zinc salt, copper salt, aluminum salt, magnesium salt, calcium salt and barium salt. Specific examples of the monocarboxylic acid include rosins (E1), naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, trimethylisobutenylcyclohexenecarboxylic acid, isononanoic acid, neodecanoic acid, versatic acid, stearic acid, and hydroxystearic acid. Examples thereof include acids, palmitic acids, oleic acids, linoleic acids, linolenic acids, pimaric acids, avietic acids and neoavietic acids. Among these, rosins (E1) are preferable from the viewpoint that a coating film having excellent crack resistance and long-term antifouling property can be easily obtained.

Examples of the rosins (E1) include rosins such as gum rosin, wood rosin and tall oil rosin; rosin derivatives such as hydrogenated rosin, disproportionated rosin and rosin metal salt, and pineapple.
The monocarboxylic acid compound (E) may be used alone or in combination of two or more.
The mass ratio of the monocarboxylic acid compound (E) to the total of the silyl ester-based polymer (A) and the acrylic-based polymer (B) in the composition (I) (polymer (A) and polymer (B)). The total mass of the monocarboxylic acid compound (E)) is preferably 0.5 or more, more preferably 0.7 or more, preferably 5 or less, and more preferably 4 or less.

In particular, the mass ratio of the rosins (E1) to the total of the silyl ester-based polymer (A) and the acrylic-based polymer (B) in the composition (I) (polymer (A) and polymer (B)). The total mass of rosins (E1)) is preferably 0.7 to 4, more preferably 0.7 to 3.5, and even more preferably 0.7 to 3. In one embodiment, this mass ratio is greater than 1.5 and less than or equal to 3.5. In such an embodiment, the antifouling coating film formed from the composition (I) has adhesiveness, dynamic antifouling property, and crack resistance to a deteriorated coating film such as an antifouling coating film containing rosins. Tends to be even better.

That is, when the mass ratio is 4 or less as compared with the case where the mass ratio exceeds 4, the adhesiveness to the deteriorated coating film and the dynamic antifouling property tend to be further improved, and when the mass ratio is less than 0.7. When it is 0.7 or more, the adhesiveness to the deteriorated coating film and the crack resistance tend to be further improved. Therefore, the composition (I) satisfying the above mass ratio requirement can be directly coated on the deteriorated coating film without using, for example, a binder, and is particularly suitable for repair coating and repair applications of the deteriorated coating film. It can be said that there is.

<Other ingredients>
The composition (I) contains copper and / or a copper compound, an organic antifouling agent other than medetomidine (C), a colorant, an extender pigment, a shaker, a dehydrating agent, and a plasticizer as other components of each of the above-mentioned components. , Any one or more of resins and solvents other than the polymer (A) and the polymer (B) can be further contained.
Each component described below may be used alone or in combination of two or more.

≪Copper and / or copper compound≫
The composition (I) may contain copper and / or a copper compound as an antifouling agent from the viewpoint of further improving the antifouling property of animal species against aquatic organisms. Examples of copper include copper powder. Examples of the copper compound include copper thiocyanate and cupronickel, and copper thiocyanate is preferable. Copper (D) cuprous oxide is not classified as this copper compound, and copper pyrithione is not classified as a copper compound but as the following organic antifouling agent.

The content of copper and / or the copper compound is preferably 0.1 to 45% by mass, more preferably 1 to 35% by mass, based on 100% by mass of the total solid content of the composition (I).

≪Organic antifouling agent≫
The composition (I) preferably contains an organic antifouling agent other than medetomidine (C) as an antifouling agent. The organic antifouling agent is a component that further improves the antifouling property of the antifouling coating film.

Examples of the organic antifouling agent include metal methylions such as copper pyrithione and disulfide pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and 4-bromo-2- (4-chlorophenyl). -5- (Trifluoromethyl) -1H-pyrrole-3-carbonitrile, pyridinetriphenylboran, 4-isopropylpyridinediphenylmethylboran, N, N-dimethyl-N'-(3,4-dichlorophenyl) urea, N -(2,4,6-trichlorophenyl) maleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine, 2,4,5,6-tetrachloroisophthalo Nitrile, bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate, chloromethyl-n-octyldisulfide, N', N'-dimethyl-N-phenyl- (N-fluorodichloromethylthio) sulfamide, N', N'-dimethyl-N -Trill- (N-fluorodichloromethylthio) sulfamide, tetraalkylthium disulfide, disulfide dithiocarbamate, zincethylenebisdithiocarbamate, 2,3-dichloro-N- (2', 6'-diethylphenyl) maleimide, 2, Examples thereof include 3-dichloro-N- (2'-ethyl-6'-methylphenyl) maleimide and the like. Among these, metal pyrithions such as copper pyrithione and zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2- (4-chlorophenyl) -5- (tri). Fluoromethyl) -1H-pyrrole-3-carbonitrile, bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate is preferred, copper pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is more preferred. ..

The content of the organic antifouling agent other than medetomidine (C) is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% based on 100% by mass of the total solid content of the composition (I). It is mass%.

≪Colorant≫
As the colorant, various conventionally known organic and inorganic pigments and dyes can be used. Examples of the organic pigment include naphthol red and phthalocyanine blue. Examples of the inorganic pigment include carbon black, valve stem, barite powder, titanium white (titanium oxide), and yellow iron oxide. When the composition (I) contains a colorant, it is preferable because the hue of the antifouling coating film obtained from the composition can be arbitrarily adjusted.
The content of the colorant is preferably 0.01 to 50% by mass, more preferably 0.01 to 30% by mass, based on 100% by mass of the total solid content of the composition (I).

≪Constitution pigment≫
Examples of extender pigments include zinc oxide, talc, silica, mica, clay, potash valorite, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, and zinc sulfide. .. Among these, zinc oxide, talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, and potassium feldspar are preferable.

The composition (I) preferably contains an extender pigment, and more preferably talc, from the viewpoint of improving the physical characteristics of the coating film such as crack resistance of the obtained antifouling coating film.
The content of the extender pigment is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the total solid content of the composition (I).
The content of talc is preferably 2 to 17% by mass with respect to 100% by mass of the total solid content of the composition (I) from the viewpoint of further improving the physical properties of the coating film such as crack resistance.

≪Shaking agent≫
The rocking agent is a component that contributes to the anti-dripping property and the prevention of sedimentation of the paint.
The rocking agent (anti-waxing agent, anti-settling agent) is, for example, a salt selected from the group consisting of an amine salt of organic bentonite, Al, Ca or Zn, a stearate salt, a lecithin salt and an alkyl sulfonate; polyethylene. Waxes selected from the group consisting of waxes, polyethylene oxide waxes, amide waxes, hydrogenated castor oil waxes and polyamide waxes; synthetic fine silica.

The rocking agent prevents precipitation of solid materials such as copper and / or copper compounds, organic antifouling agents, colorants, extender pigments, and dehydrating agents during storage of antifouling paint compositions, and improves coating workability during painting. Is used for the purpose.
The content of the rocking agent is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on 100% by mass of the total solid content of the composition (I).

≪Dehydrating agent≫
Examples of the dehydrating agent include an inorganic dehydrating agent and an organic dehydrating agent. Examples thereof include synthetic zeolite and anhydrous gypsum / semi-hydrated gypsum as the inorganic dehydrating agent, and tetramethoxysilane and tetraethoxysilane as the organic dehydrating agent. Alkoxysilanes such as tetrabutoxysilane, tetraphenoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, and trimethylethoxysilane, or polyalkoxysilanes which are condensates thereof, alkyl orthoate such as methyl orthoate and ethyl orthorate. Esters can be mentioned. The dehydrating agent is used for the purpose of preventing gelation due to decomposition of the hydrolyzable resin caused by water generated during the production and / or storage of the antifouling coating composition.
The content of the dehydrating agent is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on 100% by mass of the total solid content of the composition (I).

≪Plasticizer≫
Examples of the plasticizer include n-paraffin, chlorinated paraffin, petroleum resin, ketone resin, tricresyl phosphate, polyvinyl ethyl ether, and dialkylphthalate. Among these, chlorinated paraffin, petroleum resin, and ketone resin are included. preferable. When the composition (I) contains a plasticizer, it is preferable in that the crack resistance and water resistance of the antifouling coating film obtained from the composition are further improved.

The chlorinated paraffin may have either a linear or branched molecular structure, and may be liquid or solid (powdered) under room temperature conditions.
The average number of carbon atoms in the chlorinated paraffin is preferably 8 to 30, more preferably 10 to 26 in one molecule. Such an antifouling coating composition containing chlorinated paraffin can form an antifouling coating film with few cracks and peeling. When the average number of carbon atoms is 8 or more, the effect of suppressing the occurrence of cracks is high, while when the average number of carbon atoms is 30 or less, the antifouling property is not suppressed, which is preferable.

The viscosity (unit poison, measurement temperature 25 ° C.) of the chlorinated paraffin is preferably 1 or more, more preferably 1.2 or more, and the specific gravity (25 ° C.) is preferably 1.05 to 1.80 g /. It is cm ³ , more preferably 1.10 to 1.70 g / cm ³ .

Examples of petroleum resins include C5-based, C9-based, styrene-based, dicyclopentadiene-based ones, and hydrogenated compounds thereof.
The content of the plasticizer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on 100% by mass of the total solid content of the composition (I).

<< Resins other than polymer (A) and polymer (B) >>
The composition (I) may contain resins other than the above-mentioned polymer (A) and polymer (B). Examples of the resins include polyester resin, unsaturated polyester resin, fluororesin, polybutene resin, polyurethane resin, epoxy resin, polyamide resin, and vinyl resin (vinyl chloride-based copolymer, ethylene / vinyl acetate copolymer, etc.). , Styrene / butadiene copolymer resin, alkyd resin, kumaron resin, terpenphenol resin, silicone rubber, chloride rubber and other water-insoluble or sparingly water-soluble resins.
The content of the resins is, for example, 0.01 to 100 parts by mass with respect to 100 parts by mass of the total of the polymer (A) and the polymer (B).

≪Solvent≫
The composition (I) may contain a solvent such as water or an organic solvent, if necessary, in order to improve the dispersibility of each component and adjust the viscosity of the composition. The solvent may be the polymer (A) or the solvent used in preparing the polymer (B), and the polymer (A) and the polymer (B) are mixed with other components as necessary. This may be a solvent added separately when the antifouling coating composition is prepared. As the solvent, an organic solvent is preferable. Examples of the organic solvent include the organic solvents described in the item of <Method for producing polymer>.

When the composition (I) contains a solvent, the content thereof is preferably determined by the desired viscosity according to the coating form of the coating composition. The content of the solvent in the composition (I) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. If the content of the solvent is too large, problems such as deterioration of the sagging prevention property may occur.

<Manufacturing method of antifouling paint composition>
The composition (I) is produced by appropriately using a known method except that the polymer (A), the polymer (B), medetomidine (C) and a specific amount of cuprous oxide (D) are used. be able to. For example, the polymer (A), the polymer (B), the medetomidin (C), a specific amount of cuprous oxide (D), and optionally the monocarboxylic acid compound (E) and / or the other above. The components may be added to the stirring container at once or in any order, and each component may be mixed by a known stirring / mixing means and dispersed or dissolved in a solvent for production.

Examples of the stirring / mixing means include a paint shaker, a high-speed disperser, a sand grind mill, a basket mill, a ball mill, a three-roll roll, a loss mixer, a planetary mixer, and a universal Shinagawa stirrer.

[Use of antifouling paint composition]
The antifouling coating film of the present embodiment (hereinafter, also referred to as "antifouling coating film (J)") is formed from the composition (I). The base material with an antifouling coating film (hereinafter, also referred to as "antifouling base material (K)") of the present embodiment has a base material and an antifouling coating film (J) provided on the surface of the base material. ..

The method for producing the antifouling base material (K) includes a step of applying or impregnating the base material (object, object to be coated) with the composition (I), and the composition (I) contains a solvent. In some cases, it further comprises a step of drying the coated or impregnated body obtained by coating or impregnating the substrate.

For the coating, for example, a known method such as an air spray, an airless spray, a brush, or a roller can be used.
The composition (I) coated or impregnated by the above-mentioned method is, for example, under the conditions of −5 to 30 ° C., preferably for about 1 to 14 days, more preferably about 1 to 7 days, more preferably about 1 to 5 days. By leaving it to some extent, it dries and an antifouling coating film (J) can be obtained. The composition (I) may be dried while being blown under heating.

Alternatively, the antifouling base material (K) forms an antifouling coating film (J) from the composition (I) on the surface of the temporary base material, and the antifouling coating film (J) is peeled off from the temporary base material. It can also be manufactured by attaching it to a base material to be antifouled. At this time, the antifouling coating film (J) may be attached onto the base material via the adhesive layer.

The surface of the base material may be primer-treated, and has a layer formed on the surface thereof from various resin-based paints such as epoxy resin-based paints, vinyl resin-based paints, acrylic resin-based paints, and urethane resin-based paints. You may be doing it. Further, the base material may be an antifouling base material having an antifouling coating film, and for example, an antifouling coating film having a deteriorated antifouling coating film such as a zinc acrylic resin-based antifouling coating film containing rosins. It may be a dirty substrate. In this case, the surface of the base material on which the antifouling coating film (J) is provided means the surface after the primer treatment, the surface of the layer formed from the coating material, and the surface of the antifouling coating film.

The base material is not particularly limited, but the composition (I) is preferably used for long-term antifouling of the base material in a wide range of industrial fields such as ships, fisheries, and underwater structures. Therefore, the base material includes, for example, ships (eg, container ships, large steel ships such as tankers, fishing ships, FRP ships, wooden ships, hull skins such as yachts, and any of these new ships or repair ships. ), Underwater structures (eg oil pipelines, headraces, circulating water pipes, water supply and drainage ports of factories and thermal and nuclear power plants, submarine cables, seawater utilization equipment (seawater pumps, etc.), mega floats, bay roads, submarine tunnels. , Port facilities, various underwater civil engineering structures in canals, waterways, etc.), fishing materials (eg ropes, fishing nets, fishing gear, floats, buoys), water supply and drainage pipes for seawater, etc. in factories and thermal power / nuclear power plants, etc. , Diver suits, underwater glasses, oxygen bombs, swimwear, torpedoes, etc. Among these, ships, underwater structures, fishery materials and water supply / drainage pipes are preferable, ships and underwater structures are more preferable, and ships are particularly preferable.

In producing the antifouling base material (K), when the base material is a fishing net or a steel plate, the composition (I) may be directly applied to the surface of the base material, and when the base material is a fishing net, the composition (I) may be applied directly. The surface may be impregnated with the composition (I), and when the base material is a steel plate, a base material such as a rust preventive or a primer is applied to the surface of the base material in advance to form a base layer, and then the base layer is formed. The composition (I) may be applied to the surface of the underlayer. Further, like a steel plate having a deteriorated antifouling coating film (eg, a deteriorated coating film of a zinc-acrylic resin-based antifouling coating film containing rosins), the antifouling coating film (J) or a conventional antifouling coating film is used. An antifouling coating film (J) may be further formed on the surface of the base material on which (eg, a deteriorated coating film of a zinc-acrylic resin-based antifouling coating film containing rosins) is formed for the purpose of repair. ..

The thickness of the antifouling coating film (J) is not particularly limited, but is, for example, about 30 to 1000 μm. When the composition (I) is applied onto the base material to form the antifouling coating film (J), the thickness of the antifouling coating film (J) formed by one coating (composition). When (I) contains a solvent, the thickness of the coating film after removing the solvent) is preferably 10 to 300 μm, more preferably 30 to 200 μm, and is applied once to multiple times. Can be mentioned.

A ship having an antifouling coating film (J) can prevent a decrease in ship speed and an increase in fuel consumption due to the ability to prevent the adhesion of aquatic organisms. The underwater structure having the antifouling coating film (J) can maintain the function of the underwater structure for a long period of time because it can prevent the adhesion of aquatic organisms for a long period of time. A fishing net having an antifouling coating film (J) can prevent blockage of the net due to the ability to prevent the adhesion of aquatic organisms. Further, the water supply / drainage pipe having the antifouling coating film (J) on its inner surface can prevent the water supply / drainage pipe from being blocked and the flow velocity from being lowered due to the fact that the adhesion and reproduction of aquatic organisms can be prevented.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following Examples and Comparative Examples, "parts" indicates "parts by mass".

[Measurement condition]
Gel permeation chromatography (GPC) was measured on the polymer, and the content of the heating residue was measured on the polymer solution. Each measurement condition is as follows.

<GPC measurement conditions>
Equipment: "HLC-8320GPC" (manufactured by Tosoh Corporation)
Column: "TSKgel guardgroup SuperMP (HZ) -M + TSKgel SuperMultipore HZ-M + TSKgel SuperMultipore HZ-M" (both manufactured by Tosoh Corporation)
Eluent: tetrahydrofuran (THF)
Flow velocity: 0.35 ml / min
Detector: RI
Column constant temperature bath temperature: 40 ° C
Calibration curve: Standard polystyrene and styrene monomer Sample preparation method: After diluting the polymer solution obtained in each production example with THF, the filtrate obtained by filtering with a membrane filter was used as a GPC measurement sample.

<Measuring conditions for solid content (heat residue) content>
The polymer solution was weighed in a metal test dish of known mass and spread evenly on the bottom surface. It was heated in a hot air dryer at a temperature of 105 to 110 ° C. for 3 hours to remove volatile components. After taking out and cooling to room temperature (example: 23 ° C.), the mass of the obtained non-volatile component (heating residue) was weighed, and the solid content content was calculated from the following formula.
Content of solid content (heated residue) (%) = heated residue (g) x 100 / mass of polymer solution weighed (g)

[Example of polymer production]
[Production Example 1] Production of a solution of the silyl ester polymer (A))
43 parts of xylene and 10 parts of triisopropylsilylmethacrylate were charged in a reaction vessel equipped with a stirrer, a condenser, a thermometer, a nitrogen introduction tube and a dropping device, and heated and stirred so that the liquid temperature became 80 ° C. in a nitrogen atmosphere. went. Polymerizing with monomers (50 parts of triisopropylsilyl methacrylate, 25 parts of 2-methoxyethyl methacrylate, 10 parts of methyl methacrylate, 5 parts of n-butyl acrylate) in the reaction vessel while maintaining the same conditions. A mixture with the initiator (1.35 parts of 2,2'-azobis (isobutyronitrile)) was added dropwise over 2 hours. Then, after continuing heating and stirring at the same temperature for 1 hour and at a liquid temperature of 88 ° C. for 1 hour, the liquid temperature was raised to 95 ° C. While maintaining the same temperature, 0.1 part of 2,2'-azobis (isobutyronitrile) was added every 30 minutes a total of 4 times, and then the liquid temperature was raised to 105 ° C. After continuing heating and stirring at the same temperature for 30 minutes, 23.7 parts of xylene was added to the reaction vessel to obtain a solution of the silyl ester polymer (A-1).

The same operation as above was performed except that the monomers were changed as shown in Table 1, and the solution of the silyl ester polymer (A-2) and the solution of the silyl ester polymer (cA-1) for comparison were performed. Got

[Production Example 2] Production of solution of acrylic polymer (B) 66.7 parts of xylene is charged in a reaction vessel equipped with a stirrer, a condenser, a thermometer, a nitrogen introduction tube and a dropping device, and the liquid temperature is set in a nitrogen atmosphere. Was heated and stirred so that the temperature reached 110 ° C. While maintaining the same conditions, the monomers (50 parts styrene, 15 parts methyl methacrylate, 25 parts n-butyl acrylate, 10 parts glycidyl methacrylate) and the polymerization initiator (1.5 parts) were placed in the reaction vessel from the dropping device. A mixture of parts 2,2'-azobis (2-methylbutyronitrile) and part tert-butylperoxybenzoate) was added dropwise over 3 hours, then at the same temperature for 1 hour and at 120 ° C. for 1 hour. After continuing heating and stirring at 130 ° C. for 1 hour, 7.16 parts of xylene was added to the reaction vessel to obtain a solution of the acrylic polymer (B-1).

The same operation as above was performed except that the monomers were changed as shown in Table 2, and the solutions of the acrylic polymers (B-2) to (B-4) and the acrylic polymer for comparison (cB-) were used. 1)-(cB-2) solutions were obtained.

The weight average molecular weights of these silyl ester-based polymers and acrylic-based polymers, and the solid content (heated residue) content of these solutions are shown in Tables 1 and 2. The numerical value of the monomer indicates the blending amount (part by mass).

[Preparation of antifouling paint composition]
[Example 1]
The antifouling paint composition was prepared as follows.
To a plastic vessel, 0.1 parts of medetomidine (Selektope®) and 0.9 parts of methoxypropanol (PGM) were added and mixed using a paint shaker until the medetomidine was uniformly dissolved. To the resulting solution, 14.0 parts of xylene and 6.5 parts of gum rosin (Chinese gum rosin WW) were added and mixed again using a paint shaker until the rosin was uniformly dissolved. Then, 12.0 parts of the solution of the silyl ester polymer (A-1) and 5.0 parts of the solution of the acrylic polymer (B-1) were added to the obtained solution to make them uniform. Stir until mixed, then 10 parts zinc oxide (3 types of zinc oxide), 37 parts cuprous oxide (NC-301), 2.0 parts titanium oxide (Typake R-930), 1 .5 parts valve handle (TODA COLOR NM-50), 6.0 parts talc (FC-1), 1.0 part copper pyrithione (Copper Polymer Power), 2.0 parts polyethylene oxide wax (Disparon 4200-20X) and 0.5 parts of tetraethoxysilane (ethyl silicate 28) were added, and 200 parts of glass beads were further added, and the mixture was stirred and dispersed using a paint shaker for 1 hour. To the obtained dispersion, 1.5 parts of amido wax (Disparon A630-20X) was added, and these were stirred and dispersed for 20 minutes, and then the glass beads were removed from the mixture with an 80 mesh filtration net. An antifouling paint composition was prepared.

[Examples 2 to 19, Comparative Examples 1 to 7]
An antifouling coating composition was prepared in the same manner as in Example 1 except that the type and blending amount of each component were changed as shown in Table 3.

[Evaluation of physical properties of antifouling paint composition]
The physical characteristics of the coating film formed by using the antifouling coating composition obtained in Examples and Comparative Examples were evaluated as follows. The results obtained are shown in Table 3.

<Crack resistance>
Epoxy-based anticorrosion paint (trade name "Banno 500", manufactured by China Paint Co., Ltd., hereinafter "Epoxy 1") using air spray on a sandblasted steel plate with dimensions of 300 mm in length, 100 mm in width, and 2.3 mm in thickness. To a dry film thickness of 150 μm, and dried at 23 ° C. for 1 week to form a cured coating film. Next, using an air spray on the cured coating film of epoxy 1, an epoxy-based binder paint (trade name "Banno 500N", manufactured by China Paint Co., Ltd., hereinafter referred to as "epoxy 2") is applied with a dry film thickness of 100 μm. It was applied so as to be, and dried at 23 ° C. for 24 hours.

Next, each composition prepared in Examples and Comparative Examples was applied to the surface of the cured coating film of the epoxy 2 so as to have a dry film thickness of 200 μm, and then dried at 23 ° C. for 7 days to provide an antifouling coating film. Was formed to prepare a crack resistance test plate.

The prepared crack resistance test plate was immersed in natural seawater heated to 50 ° C. for 6 months, and the presence or absence of cracks (area standard) was confirmed.
Evaluation criteria (evaluation based on the ratio of the area of cracks to the total area of the coating film surface. 4 or more passed.)
5: No cracks are confirmed.
Cracks are confirmed in the portion of less than 4: 2%.
Cracks are confirmed in the portion of 3: 2% or more and less than 30%.
Cracks are confirmed in the portion of 2:30% or more and less than 80%.
Cracks are confirmed in the portion of 1:80% or more.

<Adhesion to deteriorated coating film>
Epoxy 1 was coated with a dry film thickness of 150 μm and epoxy 2 was coated with a dry film thickness of 100 μm in the same procedure as in the crack resistance test on a sandblasted steel sheet having dimensions of 300 mm in length, 100 mm in width, and 3.2 mm in thickness. .. A zinc acrylic antifouling paint 1 containing rosin (the rosin content is 6% by mass with respect to 100% by mass of the solid content of the antifouling paint) is applied to the surface of the cured coating film formed from the epoxy 2. It was painted to a thickness of 200 μm and dried at 23 ° C. for 7 days. The plate was immersed in seawater for one year on a test raft. The plate was pulled up and washed with water at a pressure of ^{80 kgf / cm 2.} After drying, the surface of the deteriorated coating film 1 formed from the zinc-acrylic antifouling paint 1 is coated with the antifouling paint composition prepared in Examples or Comparative Examples so as to have a dry film thickness of 200 μm, and the temperature is 23 ° C. To form an antifouling coating film, the adhesiveness test plate 1 to the deteriorated coating film 1 was prepared. The plate was immersed in natural seawater at 23 ° C. for 10 months and then dried at 23 ° C. for 1 day. After that, it basically conforms to JIS K 5600-5-6 (1999), but regardless of the dry film thickness, a grid peeling test (cross-cut method) of 25 squares of 4 mm x 4 mm was carried out, and the test target area. On the other hand, the adhesiveness was evaluated based on the area of the remaining coating film.

Evaluation criteria (4 or more passed)
5: Peeling area less than 5% 4: Peeling area 5% or more and less than 10% 3: Peeling area 10% or more and less than 40% 2: Peeling area 40% or more and less than 70% 1: Peeling area 70% or more and less than 100%

As the deteriorated coating film, instead of the zinc-acrylic antifouling paint 1, the zinc-acrylic antifouling paint 2 containing no rosin and the silyl-based antifouling paint 3 containing rosin (the rosin content is the antifouling paint 3). 7% by mass with respect to 100% by mass of solid content) and a silyl-based antifouling paint 4 containing rosin (the rosin content is 2% by mass with respect to 100% by mass of solid content of the antifouling paint 4). Then, a test plate was prepared in the same manner as in the above-mentioned zinc acrylic antifouling paint 1. These test plates are immersed in seawater for one year in a test sill, washed with water in the same manner as above, and formed from the deteriorated coating film 2 formed from the zinc acrylic antifouling paint 2 and the silyl antifouling paint 3. The surface of the deteriorated coating film 3 formed from the deteriorated coating film 3 and the silyl-based antifouling paint 4 was coated with the antifouling coating composition prepared in Examples or Comparative Examples so as to have a dry film thickness of 200 μm. , 23 ° C. was dried for 7 days to form an antifouling coating film, and adhesion test plates 2 to 4 for deteriorated coating films 2 to 4 were prepared. Then, these plates were immersed in artificial seawater at 40 ° C. for 6 months, and the adhesiveness was evaluated in the same manner as described above.

<Dynamic antifouling property>
A dynamic antifouling test plate was produced using a sandblasted steel plate having dimensions of 150 mm in length, 70 mm in width, and 1.6 mm in thickness in the same procedure as the crack resistance test plate. The obtained test plate was immersed in seawater off the coast of Kure, Hiroshima Prefecture, and a water flow was generated at about 15 knots per hour using a rotating rotor, and the water flow was applied to the antifouling coating surface of the test plate for 12 months. , The ratio of the area of the area where aquatic organisms adhered to the surface of the antifouling coating film of the test plate was evaluated by visual observation.

Evaluation criteria (4 or more passed)
5: No deposits are found.
Adhesion of slime is observed in the portion of less than 4:10%.
Adhesion of slime is observed in the portion of 3:10% or more and less than 60%.
2: Adhesion of slime is observed in the portion of 60% or more and less than 90%.
Adhesion of slime is observed in the portion of 1: 90% or more.

[Evaluation of storage stability of antifouling paint composition]
The storage stability of the antifouling coating composition obtained in Examples and Comparative Examples was evaluated as follows. The results obtained are shown in Table 4.

<Storage stability>
Each of the antifouling coating compositions of some Examples and Comparative Examples prepared by the above method was measured for initial viscosity one day after preparation and then stored at 50 ° C. for 2 months. The viscosity of each composition after storage was measured, and the viscosity increase rate obtained by the following formula was calculated. If the viscosity increase rate is less than 20%, it is passed.
An antifouling coating composition having a viscosity increase rate of 20% or more causes problems such as a significant decrease in coating workability, an increase in the amount of organic solvent for dilution, and an increase in environmental load.
Viscosity increase rate = (viscosity after storage-initial viscosity) / initial viscosity x 100

The details of the components used in the examples and comparative examples are as follows.

Claims (10)

A silyl ester-based polymer (A) having a structural unit (a-1) derived from the polymerizable monomer (a1) represented by the formula (a1), and a silyl ester-based polymer (A).
An acrylic polymer (B) having a structural unit (b-1) derived from glycidyl (meth) acrylate, and
With medetomidine (C),
An antifouling coating composition containing cuprous oxide (D).
An antifouling coating composition in which the content of the cuprous oxide (D) is more than 0% by mass and 55% by mass or less in the solid content of the antifouling coating composition.
R ¹ −CH = C (CH ₃ ) −COO− (SiR ² R ³ O) _{n −} ^{SiR 4} R ⁵ R ⁶ … (a1)
[In the formula (a1), R ^{2 to} R ⁶ are monovalent organic groups having 1 to 20 carbon atoms which may independently have heteroatoms. n is an integer greater than or equal to 0 or 1. R ¹ is a hydrogen atom or ^{a group represented by R 7} −OC (= O) −, and R ⁷ is a monovalent group having 1 to 20 carbon atoms which may have a hydrogen atom or a hetero atom. It is an organic group or a silyl group represented by ^{R 8} R ⁹ R ^{10 Si−, and R 8} , R ⁹ and R ¹⁰ are monovalents having 1 to 20 carbon atoms which may independently have heteroatoms. It is an organic group of. ] The antifouling coating composition according to claim 1, further containing the monocarboxylic acid compound (E). The antifouling coating composition according to claim 2, wherein the monocarboxylic acid compound (E) is a rosin (E1). Mass ratio of the rosins (E1) to the total of the silyl ester polymer (A) and the acrylic polymer (B) (total mass of the polymer (A) and the polymer (B) / rosins) The antifouling coating composition according to claim 3, wherein the mass ratio of (E1) is 0.7 to 4. The antifouling coating composition according to any one of claims 1 to 4, further containing talc and having a talc content of 2 to 17% by mass in the solid content of the antifouling coating composition. The antifouling coating composition according to any one of claims 1 to 5, which is used for repairing a deteriorated coating film of an antifouling coating film. An antifouling coating film formed from the antifouling coating composition according to any one of claims 1 to 6. With the base material
A base material with an antifouling coating film having the antifouling coating film according to claim 7, which is provided on the surface of the base material. The base material with an antifouling coating film according to claim 8, wherein the base material is at least one selected from ships, underwater structures, fishery materials, and water supply / drainage pipes. A method for producing a base material with an antifouling coating film, which comprises a step of applying or impregnating the base material with the antifouling coating composition according to any one of claims 1 to 6.