KR20200142533A - Antifouling paint composition - Google Patents

Abstract

(식 중, R¹은 수소 또는 메틸기, R², R³, R⁴는 탄소수 3 ~ 8의 분기상 알킬기, 페닐기로부터 선택되고, 동일하거나 서로 다르다)
상기 공중합체(A)는 이하의 요건 (A1) ~ (A2)를 충족하고,
상기 공중합체(B)는 이하의 요건 (B1) ~ (B2)를 충족하는, 방오 도료 조성물이 제공된다.
(A1) 상기 단량체(a)의 함유량이 상기 단량체(a)와 상기 단량체(b)의 총 질량에 대하여 30 ~ 50질량%이다.
(A2) 상기 단량체(b) 중 아크릴산 2-메톡시에틸의 함유량이 상기 단량체(a)와 상기 단량체(b)의 총 질량에 대하여 15 ~ 30질량%이다.
(B1) 상기 단량체(a)의 함유량이 상기 단량체(a)와 상기 단량체(b)의 총 질량에 대하여 30 ~ 40질량%이다.
(B2) 상기 단량체(b) 중 메타크릴산 2-메톡시에틸의 함유량이 상기 단량체(a)와 상기 단량체(b)의 총 질량에 대하여 30 ~ 50질량%이다.There is provided a composition for forming an antifouling coating film with high environmental safety, capable of exhibiting good antifouling performance even at a draft portion where the coating film is dissolved for a long period of time even after exposure to sunlight for a long period of time and adhesion of aquatic fouling organisms is likely to occur.
[Solution means] According to the present invention, as an antifouling coating composition containing a copolymer (A), a copolymer (B), and an antifouling agent, the copolymers (A) and (B) are each a monomer (a) And, obtained by copolymerizing a mixture of a polymerizable unsaturated monomer (b) other than the monomer (a), wherein the monomer (a) is represented by the general formula (1),
General Formula (1):

(Wherein, R ¹ is hydrogen or a methyl group, R ² , R ³ , R ⁴ are selected from a C 3 to C 8 branched alkyl group, a phenyl group, and the same or different)
The copolymer (A) satisfies the following requirements (A1) to (A2),
The copolymer (B) is provided with an antifouling coating composition satisfying the following requirements (B1) to (B2).
(A1) The content of the monomer (a) is 30 to 50% by mass based on the total mass of the monomer (a) and the monomer (b).
(A2) The content of 2-methoxyethyl acrylate in the monomer (b) is 15 to 30 mass% with respect to the total mass of the monomer (a) and the monomer (b).
(B1) The content of the monomer (a) is 30 to 40 mass% based on the total mass of the monomer (a) and the monomer (b).
(B2) The content of 2-methoxyethyl methacrylate in the monomer (b) is 30 to 50 mass% with respect to the total mass of the monomer (a) and the monomer (b).

Description

Antifouling paint composition

The present invention relates to an antifouling coating composition.

Aquatic contaminated organisms such as barnacles, western tubeworms, pearl mussels, moss insects (Bugula neritina), snails, greens, snails, slime, etc. By being attached to the underwater structure of the ship, there are problems such as impairing the functions of these ships and damaging the appearance.

In order to prevent such a problem, a technique is known in which an antifouling coating composition is applied to a ship or the like to form an antifouling coating film, and the antifouling agent is gradually released from the antifouling coating film, thereby exhibiting antifouling performance over a long period of time (Patent Document 1).

Japanese Patent Laid-Open Publication No. 2000-17203

However, even if the technology of Patent Document 1 is adopted, the coating portion that is always immersed in seawater maintains antifouling performance for a long period of time, but various influences such as repeated wet and dry conditions in the draft, which is the boundary between water and water, are susceptible to sunlight, etc. There was a problem that the antifouling property was not sufficiently exhibited from receiving.

The present invention has been made in view of these circumstances, and the coating film dissolution continues for a long period of time even after exposure to sunlight for a long period of time, and excellent antifouling performance can be exhibited even at a draft portion where adhesion of aquatic fouling organisms is likely to occur. It is to provide a composition for forming a coating film.

According to the present invention, as an antifouling coating composition containing a copolymer (A), a copolymer (B), and an antifouling agent, the copolymers (A) and (B) are each a monomer (a) and a monomer (a) ) Obtained by copolymerizing a mixture of a polymerizable unsaturated monomer (b) other than the), the monomer (a) is represented by the general formula (1),

General Formula (1):

[Formula 1]

(Wherein, R ¹ is hydrogen or a methyl group, R ² , R ³ , R ⁴ are selected from a C 3 to C 8 branched alkyl group, a phenyl group, and the same or different)

The copolymer (A) satisfies the following requirements (A1) to (A2),

The copolymer (B) is provided with an antifouling coating composition satisfying the following requirements (B1) to (B2).

(A1) The content of the monomer (a) is 30 to 50% by mass based on the total mass of the monomer (a) and the monomer (b).

(A2) The content of 2-methoxyethyl acrylate in the monomer (b) is 15 to 30 mass% based on the total mass of the monomer (a) and the monomer (b).

(B1) The content of the monomer (a) is 30 to 40 mass% based on the total mass of the monomer (a) and the monomer (b).

(B2) The content of 2-methoxyethyl methacrylate in the monomer (b) is 30 to 50 mass% based on the total mass of the monomer (a) and the monomer (b).

As the inventors have conducted intensive studies, a copolymer (A) obtained by copolymerizing a mixture containing a silyl ester monomer and 2-methoxyethyl acrylate in a specific amount, and a silyl ester monomer and 2-methoxyethyl methacrylate When an antifouling coating film was formed using a composition containing a copolymer (B) obtained by copolymerizing a mixture each containing a specific amount, it was found that good antifouling performance was exhibited even at the draft, and the present invention was completed.

Hereinafter, the present invention will be described in detail.

1. Antifouling paint composition

The antifouling coating composition of the present invention contains a copolymer (A), a copolymer (B), and an antifouling agent.

1-1. Copolymers (A) and (B)

Copolymers (A) and (B) are each a (meth)acrylic acid triorganosilyl ester copolymer, obtained by copolymerizing a mixture of a monomer (a) and a polymerizable unsaturated monomer (b) other than the monomer (a). I can. Thus, the copolymers (A) and (B) contain monomer units derived from monomers (a) and (b), respectively. The compound contained in the monomer (a) and the compounding ratio thereof may be the same or different in the copolymers (A) and (B). The compound contained in the monomer (b) may be the same or different in the copolymer (A) and (B). When the compound contained in the monomer (b) is the same in the copolymer (A) and (B), the blending ratio is different.

<Monomer (a)>

The monomer (a) is a (meth)acrylic acid triorganosilyl ester monomer, and is represented by General Formula (1).

General Formula (1):

[Formula 1]

(Wherein, R ¹ is hydrogen or a methyl group, R ² , R ³ , R ⁴ are selected from a C 3 to C 8 branched alkyl group, a phenyl group, and the same or different)

In the present invention, as the monomer (a) represented by the general formula (1), for example, triisopropylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tris-butylsilyl (meth)acrylate, Triisoamylsilyl (meth)acrylate, tris(2-ethylhexyl)silyl (meth)acrylate, triphenylsilyl (meth)acrylate, diisopropylisobutylsilyl (meth)acrylate, diisopropylisoa (meth)acrylate Milsilyl, diisopropyl (2-ethylhexyl)silyl (meth)acrylate, diisopropylphenylsilyl (meth)acrylate, diisopropylcyclohexylsilyl (meth)acrylate, t-butyldiisopropylsilyl (meth)acrylate , T-butyldiisobutylsilyl (meth)acrylate, t-butyldiisoamylsilyl (meth)acrylate, t-butyldiphenylsilyl (meth)acrylate, and the like, preferably triiso (meth)acrylate It is propylsilyl, particularly preferably triisopropylsilyl methacrylate. Each of these monomers is used as one or two or more.

<Monomer (b)>

The monomer (b) is a monomer copolymerizable with the monomer (a), and examples thereof include the following. Methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate , Cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-(meth)acrylate Methoxypropyl, 4-methoxybutyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, polyethylene glycol methyl ether (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc. Of (meth)acrylic acid esters.

Zinc versatic acid (meth)acrylate, magnesium versatic acid (meth)acrylate, copper versatic acid (meth)acrylate, zinc octylate (meth)acrylate, magnesium octylate (meth)acrylate, copper octylate (meth) )Acrylate, zinc laurate (meth)acrylate, magnesium laurate (meth)acrylate, copper laurate (meth)acrylate, zinc stearate (meth)acrylate, magnesium stearate (meth)acrylic (Meth)acrylic acid metal pendants such as acrylate and copper stearate (meth)acrylate, and metal (meth)acrylates such as zinc (meth)acrylate and copper (meth)acrylate.

A vinyl compound having a functional group such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone.

Aromatic compounds such as styrene, vinyl toluene, and α-methyl styrene.

Dialkyl ester compounds of unsaturated dibasic acids, such as dimethyl maleate, dibutyl maleate, and dimethyl fumarate.

The monomers (b) are used in one or two or more types, respectively, and are preferably (meth)acrylic acid esters.

<Requirements (A1) to (A2) and (B1) to (B2)>

In the present invention, it is an essential requirement that the copolymer (A) satisfies the requirements (A1) to (A2) and that the copolymer (B) satisfies the requirements (B1) to (B2).

(A1) The content of the monomer (a) is 30 to 50% by mass based on the total mass of the monomer (a) and the monomer (b).

(A2) The content of 2-methoxyethyl acrylate in the monomer (b) is 15 to 30 mass% with respect to the total mass of the monomer (a) and the monomer (b).

(B1) The content of the monomer (a) is 30 to 40 mass% based on the total mass of the monomer (a) and the monomer (b).

(B2) The content of 2-methoxyethyl methacrylate in the monomer (b) is 30 to 50 mass% with respect to the total mass of the monomer (a) and the monomer (b).

Notable points are:

(1) The content of the monomer (a) is 30 to 50 mass% in the copolymer (A) and 30 to 40 mass% in the copolymer (B), all of which are relatively small amounts.

(2) In the copolymer (A), the monomer (b) contains 2-methoxyethyl acrylate, and in the copolymer (B), the monomer (b) contains 2-methoxyethyl methacrylate.

As described above, the present invention uses two types of copolymers having a relatively small ratio of silyl ester monomer units, one of which contains 2-methoxyethyl acrylate and the other is 2-methoxyethyl methacrylate. It is characterized by including a unit. And, as shown in Examples to be described later, by having these characteristics, the hydrophilicity of the coating film is improved, the adhesion of the coating film to a highly polarized surface such as glass is improved, and resistance in wet and dry cycle tests is improved. Achieve technical effect. This is the same as the technical effect of improving the adhesion when applying a paint to the surface of the old coating film.

In the requirement (A1), the content of the monomer (a) is, for example, 30, 35, 40, 45, 50 mass% with respect to the total mass of the monomer (a) and the monomer (b), and any two exemplified herein It may be within the range between values.

In the requirement (A2), the content of 2-methoxyethyl acrylate is, for example, 15, 20, 25, 30 mass% based on the total mass of the monomer (a) and the monomer (b), and any 2 exemplified herein It may be within the range between the number of values. The monomer (b) of the copolymer (A) may contain 2-methoxyethyl methacrylate, but its content is greater than the content of 2-methoxyethyl methacrylate in the monomer (b) of the copolymer (B). A small amount is preferable, and 1/2 or less of the content of 2-methoxyethyl methacrylate in the monomer (b) of the copolymer (B) is preferable. It is preferable that the monomer (b) of the copolymer (A) does not contain 2-methoxyethyl methacrylate.

In the requirement (B1), the content of the monomer (a) is, for example, 30, 35, 40 mass% with respect to the total mass of the monomer (a) and the monomer (b), and the range between any two values exemplified herein It may be mine.

In the requirement (B2), the content of 2-methoxyethyl methacrylate is, for example, 30, 35, 40, 45, 50 mass% with respect to the total mass of the monomer (a) and the monomer (b), exemplified here It may be within a range between any two values. The monomer (b) of the copolymer (B) may contain 2-methoxyethyl acrylate, but the content thereof is preferably less than the content of 2-methoxyethyl acrylate in the monomer (b) of the copolymer (A). , 1/2 or less of the content of 2-methoxyethyl acrylate in the monomer (b) of the copolymer (A) is preferable. It is preferable that the monomer (b) of the copolymer (B) does not contain 2-methoxyethyl acrylate.

In addition, in the copolymers (A) and (B), the monomer (b) may contain silyl esters other than the monomer (a). In this case, the content of the total silyl ester relative to the total mass of the monomers (a) and (b) is, for example, 30 to 60% by mass, specifically, for example, 30, 35, 40, 45, 50, 55 , 60% by mass, and may be within a range between any two numerical values exemplified herein. In addition, the content of the silyl ester other than the monomer (a) is preferably less than the content of the monomer (a), preferably 1/2 or less of the content of the monomer (a), and more preferably 1/5 or less.

The content of the copolymer (A) is preferably 25 to 75% by mass based on the total mass of the copolymer (A) and the copolymer (B). In this case, the effect of improving resistance in wet and dry cycle tests is remarkable. The content of the copolymer (A) is specifically, for example, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75% by mass, and a range between any two values exemplified herein It may be mine.

<Synthesis of copolymers (A) and (B)>

Copolymers (A) and (B) can be obtained by copolymerizing a mixture of a monomer (a) and a monomer (b). The copolymerization is carried out, for example, in the presence of a polymerization initiator.

It is preferable that the weight average molecular weight of the copolymers (A) and (B) is 5000-300000. If the molecular weight is less than 5000, the coating film of the antifouling paint becomes brittle, and peeling or cracking is likely to occur, and if it exceeds 300000, the viscosity of the copolymer solution increases and handling is difficult. This weight average molecular weight is specifically, for example, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, and the range between any two values exemplified herein It may be mine.

As the polymerization initiator, for example, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, dimethyl-2,2'-azobisisobutyrate Azo compounds such as; Benzoyl peroxide, di-tert-butyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexanoate, 1,1,3,3- Peroxides, such as tetramethylbutyl peroxy-2-ethylhexanoate, etc. are mentioned. These polymerization initiators can be used alone or in combination of two or more. Especially as the polymerization initiator, 2,2'-azobisisobutyronitrile and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate are preferable.

By appropriately setting the amount of the polymerization initiator used, the molecular weight of the triorganosilyl ester-containing copolymer can be adjusted.

As a polymerization method, solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc. are mentioned, for example. Among these, solution polymerization is preferred in that the copolymer can be synthesized particularly easily and with high precision.

In the polymerization reaction, an organic solvent may be used if necessary. Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene, ethyl benzene, and toluene; Aliphatic hydrocarbon solvents such as hexane and heptane; Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate; Alcohol solvents such as isopropyl alcohol and butyl alcohol; Ether solvents such as dioxane, diethyl ether, and dibutyl ether; Ketone solvents, such as methyl ethyl ketone and methyl isobutyl ketone, etc. are mentioned. Among these, aromatic hydrocarbon-based solvents are particularly preferable, and xylene is more preferable. These solvents can be used alone or in combination of two or more.

The reaction temperature in the polymerization reaction may be appropriately set depending on the type of polymerization initiator, etc., and is usually about 70 to 120°C, preferably about 70 to 100°C. The reaction time in the polymerization reaction may be appropriately set depending on the reaction temperature and the like, and is usually about 4 to 8 hours.

The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.

1-2. Antifouling agent

As an antifouling agent, an inorganic agent and an organic agent are mentioned, for example.

Examples of the inorganic drugs include copper oxide, copper thiocyanate (common name: copper rhodanide), and copper powder. Among these, copper oxide and copper rodan are particularly preferred, and copper oxide is more preferably surface-treated with glycerin, sucrose, stearic acid, lauric acid, lycithin, mineral oil or the like from the viewpoint of long-term stability during storage.

Examples of organic drugs include 2-mercaptopyridine-N-oxide copper (common name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (common name: zinc pyrithione), and zinc. Ethylene bisdithiocarbamate (common name: Zineb), 4,5-dichloro-2-n-octyl-3-isothiazolone (common name: Sea-Nine 211), 3,4 -Dichlorophenyl-NN-dimethylurea (common name: diuron), 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine (common name: Irgarol 1051) , 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (common name: ECONEA 028), 4-[1-(2,3-dimethylphenyl)ethyl] -1H-imidazole (common name: medetomidine), and the like.

These antifouling agents can be used alone or in combination of two or more.

1-3. Other additives

Further, to the resin for antifouling paints of the present invention, an antifouling paint can be obtained by adding a dissolution regulator, a plasticizer, a pigment, a dye, an antifoaming agent, a dehydrating agent, a thixotropic agent, an organic solvent, and the like, if necessary.

Examples of dissolution modifiers include monocarboxylic acids such as rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof. Acids and salts thereof, or alicyclic hydrocarbon resins. These may be used alone or in combination of two or more.

Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleinized rosin, formylated rosin, polymerized rosin, and the like. As the alicyclic hydrocarbon resin, commercially available products include, for example, Quintone 1500, 1525L, 1700 (brand name, manufactured by Nippon Xeon Corporation).

As plasticizers, for example, phosphoric acid esters, phthalic acid esters, adipic acid esters, sebacic acid esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonylpentasulfide, petrolatum, poly Butene, trimellitic acid tris (2-ethylhexyl), silicone oil, liquid paraffin, chlorinated paraffin, and the like. These can be used alone or in combination of two or more.

Examples of the dehydrating agent include synthetic zeolite adsorbents, ortho esters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, carbodiimidazoles, and the like. These can be used alone or in combination of two or more.

2. Method for producing antifouling coating composition

The antifouling coating composition of the present invention can be prepared by mixing and dispersing a mixture containing the copolymer (A), the copolymer (B), the antifouling agent, and other additives using a dispersing machine.

As the mixed liquid, it is preferable that various materials such as a copolymer and an antifouling agent are dissolved or dispersed in a solvent.

As the dispersing group, for example, those that can be used as a pulverizing group can be suitably used. For example, a commercially available homo mixer, sand mill, bead mill, or the like can be used. Moreover, you may mix and disperse the said mixed liquid using what added glass beads for mixing and dispersing etc. to a container equipped with a stirrer.

3. Antifouling treatment method, antifouling coating, and painting

In the antifouling treatment method of the present invention, an antifouling coating film is formed on the surface of an object to be coated using the antifouling coating composition. According to the antifouling treatment method of the present invention, the antifouling coating film is gradually dissolved from the surface and the surface of the coating film is constantly renewed, so that adhesion of aquatic contaminant organisms can be prevented.

Examples of the film-forming material include ships (especially the bottom of the ship), fishing tools, and underwater structures.

The thickness of the antifouling coating film may be appropriately set according to the type of the film formed, the sailing speed of the ship, and the sea water temperature. For example, when the film formation is the bottom of a ship, the thickness of the antifouling film is usually 50 to 700 μm, preferably 100 to 600 μm.

[Example]

The features of the present invention are further clarified by illustrating examples and the like below. However, the present invention is not limited to these examples.

% In each of Preparation Examples, Comparative Preparation Examples, Examples, and Comparative Examples represents mass%. The viscosity is a measured value at 25°C, and is a value determined by a B-type viscometer. The weight average molecular weight (Mw) is a value (polystyrene conversion value) calculated|required by GPC. The conditions of GPC are as follows.

Apparatus...HLC-8220GPC manufactured by Tosoh Corporation

Column...TSKgel SuperHZM-M (manufactured by Tosoh Corporation) 2 pieces

Flow...0.35 mL/min

Detector...RI

Column thermostat temperature...40°C

Eluent...THF

The heating residue is a value measured in accordance with JIS K 5601-1-2:1999 (ISO 3251:1993) "Paint component test method-heating residue".

In addition, the unit of the blending amount of each component in the table is g.

<Production Example 1 (Preparation of copolymer solution SA-1)>

After adding 400 g of xylene to a 2000 ml flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, the temperature was raised to 83 to 87° C. under a nitrogen atmosphere, and while stirring, 150 g of triisopropylsilyl methacrylate, 37 g of ethyl acrylate, A mixture of 238 g of methyl methacrylate, 75 g of 2-methoxyethyl acrylate, and 5 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta O manufactured by Nippon Oil) was added at 83 to 87°C. It was dripped for 1 hour while maintaining it. After the dropwise addition, 0.5 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added 3 times every 1 hour while maintaining at 83 to 87°C to complete the polymerization reaction, and then xylene 100 g Was added and dissolved to obtain a copolymer solution SA-1. The heating residue of the copolymer solution SA-1 was 49.8%, and the weight average molecular weight was 52000.

<Production Examples 2 to 20, and Comparative Production Examples 1 to 4>

Polymerization was carried out in the same manner as in Preparation Example 1 using the organic solvent, monomer, and polymerization initiator shown in Tables 1 to 3, and the copolymer solutions SA-2 to SA-10 and copolymer (B ) To obtain the copolymer solutions SB-1 to SB-10, and copolymer solutions T-1 to T-4 of other copolymers. The heating residue and the weight average molecular weight of each obtained copolymer solution were measured.

The results are shown in Tables 1 to 3.

<Production Example 21 (Preparation of rosin metal salt solution)>

In a flask equipped with a thermometer, a reflux cooler, and a stirrer, 240 g of Chinese gum rosin (WW) and 360 g of xylene were added to the flask, and 120 g of zinc oxide was added so that the resin acids in the rosin all form zinc salts. It was refluxed and dehydrated under reduced pressure at -80°C for 3 hours. After that, cooling filtration was performed to obtain a xylene solution (dark brown transparent liquid, solid content 50%) of the rosin zinc salt. The heating residue of the obtained solution was 50.4%.

<Production Example 22 (Preparation of hydrogenated rosin metal salt solution)>

In a flask equipped with a thermometer, a reflux cooler, and a stirrer, 240 g of HYPALE CH and 360 g of xylene were added to the flask, and 120 g of zinc oxide was added so that all resin acids in the rosin form zinc salts, and at 70 to 80°C. It was refluxed and dehydrated under reduced pressure for 3 hours. After that, cooling filtration was performed to obtain a xylene solution (dark brown transparent liquid, solid content 50%) of the rosin zinc salt. The heating residue of the obtained solution was 50.3%.

<Examples 1 to 83, and Comparative Examples 1 to 14>

Using the copolymer solutions SA-1 to SA-10, SB-1 to SB-10, and T-1 to T-4, antifouling coating compositions were prepared by the formulations shown in Tables 4 to 14.

(Wet and dry cycle test of coating film)

A test plate was obtained by coating an antifouling coating composition on a glass plate using a 400 μm applicator.

This test plate was subjected to a 12-hour 40°C freshwater immersion test and a 12-hour air exposure test for 6 months, and then visually evaluated the physical properties of the test plate.

The thing with no peeling was set as ○, and the thing with peeling was set as x.

Details of the dissolution regulators, plasticizers, antifouling agents, and other additives in Tables 4 to 14 are as follows.

<Dissolution regulator>

Rosin metal salt solution: using the one prepared in Preparation Example 21

Hydrogenated rosin metal salt solution: using the one prepared in Preparation Example 22

Gum rosin solution: 50% solids xylene solution of Chinese gum rosin (WW)

Hydrogenated gum rosin solution: 50% solid content xylene solution of the brand name "HYPALE CH" (manufactured by Arakawa Chemical Industries, Ltd.).

<plasticizer>

Chlorinated paraffin: Trade name "Paraffin Chlorinated (Cl: 40%)" (manufactured by Wako Pure Chemical Industries, Ltd.)

E-2000H: epoxidized soybean oil: brand name "SANSO CIZER E-2000H" (manufactured by Shinnihonrika Co., Ltd.)

Trimellitic acid tris (2-ethylhexyl): Trade name "Trimellitic acid tris (2-ethylhexyl)" (manufactured by Tokyo Kasei Co., Ltd.)

Hexamoll (registered trademark) DINCH (registered trademark): manufactured by BASF, a non-phthalic acid plasticizer

<Antifouling agent>

Nitrous oxide: Trade name "NC-301" (manufactured by Nissin Chemco)

Copper pyrithione: brand name "Copper omadine" (manufactured by Arch Chemical Co., Ltd.)

Zinc pyrithione: Brand name "Zinc omadine" (manufactured by Arch Chemical Co., Ltd.)

Zineb: Trade name "Zineb" (manufactured by SIGMA-ALDRICH)

SeaNine: Trade name "Sea Nine211" 4,5-dichloro-2-n-octyl-3-isothiazolone (solid content 30% xylene solution, manufactured by Rohm and Haas)

medetomidine: Trade name "4-(1-(2,3-Dimethylphenyl)ethyl)-1H-imidazole" (manufactured by Wako Junyaku Industrial Co., Ltd.)

Econea: Trade name "Econea 028"… 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)

<Other additives>

Talc (manufactured by Matsumura Industrial Co., Ltd., Crown Talc 3S)

Zinc oxide (manufactured by Seido Chemical Co., Ltd., two types of zinc oxide (brand name))

Bengala (manufactured by Toda Pigment, TODA COLOR EP-13D)

Titanium oxide (manufactured by Furugawa Machinery Metal Co., Ltd., FR-41)

Tetraethoxysilane: Trade name "Tetraethyl Orthosilicate" (manufactured by Tokyo Kasei Co., Ltd.)

Aliphatic amide thixotropic agent: brand name "DISPARLON A603-20X" (manufactured by Kusumoto Kasei Co., Ltd.)

<Consideration>

In Tables 4 to 14, the coating film formed using the coating composition (Examples 1 to 83) of the present invention has improved adhesion to the glass surface than the coating film formed using the coating composition of Comparative Examples 1 to 14, Even after the wet and dry cycle tests (after 6 months), no peeling of the coating film occurred.

On the other hand, the coating film formed using the coating composition of Comparative Examples 1 to 14 had poor adhesion to the glass surface, and peeling of the coating film occurred after wet and dry cycle tests (after 3 months).

Claims (1)

As an antifouling coating composition containing a copolymer (A), a copolymer (B), and an antifouling agent,
The copolymers (A) and (B) are each obtained by copolymerizing a mixture of a monomer (a) and a polymerizable unsaturated monomer (b) other than the monomer (a),
The monomer (a) is represented by the following general formula (1),
General Formula (1):
[Formula 1]

(Wherein, R ¹ is hydrogen or a methyl group, R ² , R ³ , R ⁴ are selected from a C 3 to C 8 branched alkyl group, a phenyl group, and the same or different)
The copolymer (A) satisfies the following requirements (A1) to (A2),
The said copolymer (B) satisfies the following requirements (B1)-(B2), Antifouling coating composition.
(A1) The content of the monomer (a) is 30 to 50% by mass based on the total mass of the monomer (a) and the monomer (b).
(A2) The content of 2-methoxyethyl acrylate in the monomer (b) is 15 to 30 mass% with respect to the total mass of the monomer (a) and the monomer (b).
(B1) The content of the monomer (a) is 30 to 40 mass% based on the total mass of the monomer (a) and the monomer (b).
(B2) The content of 2-methoxyethyl methacrylate in the monomer (b) is 30 to 50 mass% with respect to the total mass of the monomer (a) and the monomer (b).